U.S. patent application number 12/439360 was filed with the patent office on 2010-03-25 for hydrogenated norbornene-based ring-opening polymerization polymer, resin composition, and molded object.
This patent application is currently assigned to ZEON CORPORATION. Invention is credited to Takeshi Hirata, Koichi Ikeda, Teiji Kohara, Nobuhiro Kudo, Tokudai Ogawa, Haruhiko Takahashi.
Application Number | 20100076396 12/439360 |
Document ID | / |
Family ID | 39136014 |
Filed Date | 2010-03-25 |
United States Patent
Application |
20100076396 |
Kind Code |
A1 |
Takahashi; Haruhiko ; et
al. |
March 25, 2010 |
HYDROGENATED NORBORNENE-BASED RING-OPENING POLYMERIZATION POLYMER,
RESIN COMPOSITION, AND MOLDED OBJECT
Abstract
A hydrogenated norbornene ring-open polymer obtained by
hydrogenating 80% or more of main-chain carbon-carbon double bonds
of a ring-open polymer which is obtained by ring-opening
polymerization of 2-norbornene is disclosed. The hydrogenated
norbornene ring-open polymer has a weight average molecular weight
(Mw) determined by gel permeation chromatography (GPC) of 50,000 to
200,000, a molecular weight distribution (Mw/Mn) of 1.5 to 10.0,
and a melting point of 110 to 145.degree. C. Also disclosed is a
hydrogenated norbornene ring-open polymer (hydrogenated polymer)
obtained by hydrogenating 80% or more of carbon-carbon double bonds
of a ring-open polymer which is obtained by ring-opening
copolymerization of 2-norbornene and a substituent-containing
norbornene monomer, wherein the proportion of a repeating unit (A)
derived from the 2-norbornene with respect to all repeating units
is 90 to 99 wt % and the proportion of a repeating unit (B) derived
from the substituent-containing norbornene monomer with respect to
all repeating units is 1 to 10 wt %. The hydrogenated ring-open
polymer has a melting point of 110 to 145.degree. C. A resin
composition and a molding material containing these hydrogenated
polymers, a molded article, a resin film, a resin sheet, a
multilayer laminate, a packing material, a molded article for
medical supplies, a blister molding sheet, a blister molded
article, and a multilayer blow-molded container made of these
hydrogenated polymers are also disclosed.
Inventors: |
Takahashi; Haruhiko; (Tokyo,
JP) ; Kohara; Teiji; (Tokyo, JP) ; Kudo;
Nobuhiro; (Tokyo, JP) ; Ikeda; Koichi; (Tokyo,
JP) ; Ogawa; Tokudai; (Tokyo, JP) ; Hirata;
Takeshi; (Tokyo, JP) |
Correspondence
Address: |
WESTERMAN, HATTORI, DANIELS & ADRIAN, LLP
1250 CONNECTICUT AVENUE, NW, SUITE 700
WASHINGTON
DC
20036
US
|
Assignee: |
ZEON CORPORATION
Tokyo
JP
|
Family ID: |
39136014 |
Appl. No.: |
12/439360 |
Filed: |
August 31, 2007 |
PCT Filed: |
August 31, 2007 |
PCT NO: |
PCT/JP2007/067043 |
371 Date: |
June 15, 2009 |
Current U.S.
Class: |
604/408 ;
428/35.7; 428/476.3; 428/483; 428/515; 428/516; 524/553;
526/281 |
Current CPC
Class: |
Y10T 428/3175 20150401;
C08G 2261/724 20130101; B32B 27/306 20130101; B32B 27/32 20130101;
B32B 2439/80 20130101; C08G 61/08 20130101; B32B 27/365 20130101;
Y10T 428/31909 20150401; B32B 2307/306 20130101; B32B 2307/50
20130101; B32B 15/20 20130101; B32B 2439/70 20130101; Y10T
428/31797 20150401; Y10T 428/31855 20150401; B32B 2307/7242
20130101; B32B 27/08 20130101; B32B 27/36 20130101; B32B 27/325
20130101; Y10T 428/31913 20150401; B32B 27/34 20130101; B32B
2307/412 20130101; C08G 2261/3324 20130101; Y10T 428/1352 20150115;
Y10T 428/31757 20150401; B32B 2307/714 20130101; B32B 27/28
20130101; B32B 15/08 20130101; B32B 27/304 20130101; B32B 27/30
20130101; B32B 27/18 20130101; Y10T 428/31938 20150401; B32B 27/286
20130101; Y10T 428/1345 20150115; B32B 2307/558 20130101; B32B
27/302 20130101 |
Class at
Publication: |
604/408 ;
526/281; 524/553; 428/515; 428/476.3; 428/483; 428/516;
428/35.7 |
International
Class: |
A61J 1/10 20060101
A61J001/10; C08F 132/08 20060101 C08F132/08; C08L 55/00 20060101
C08L055/00; B32B 27/08 20060101 B32B027/08; B32B 1/00 20060101
B32B001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 31, 2006 |
JP |
2006-236627 |
Aug 31, 2006 |
JP |
2006-237000 |
Sep 29, 2006 |
JP |
2006-266680 |
Sep 29, 2006 |
JP |
2006-266683 |
Sep 29, 2006 |
JP |
2006-266889 |
Sep 29, 2006 |
JP |
2006-269332 |
Dec 20, 2006 |
JP |
2006-342808 |
Dec 20, 2006 |
JP |
2006-342872 |
Dec 28, 2006 |
JP |
2006-355191 |
Claims
1. A hydrogenated norbornene ring-open polymer obtained by
hydrogenating 80% or more of main-chain carbon-carbon double bonds
of a ring-open polymer which is obtained by ring-opening
polymerization of 2-norbornene, the hydrogenated norbornene
ring-open polymer having a weight average molecular weight (Mw)
determined by gel permeation chromatography (GPC) of 50,000 to
200,000, a molecular weight distribution (Mw/Mn) of 1.5 to 10.0,
and a melting point of 110 to 145.degree. C.
2. A hydrogenated norbornene ring-open polymer obtained by
hydrogenating 80% or more of carbon-carbon double bonds of a
ring-open polymer which is obtained by ring-opening
copolymerization of 2-norbornene and a substituent-containing
norbornene monomer, the proportion of a repeating unit (A) derived
from the 2-norbornene with respect to all repeating units being 90
to 99 wt % and the proportion of a repeating unit (B) derived from
the substituent-containing norbornene monomer with respect to all
repeating units being 1 to 10 wt %, and the hydrogenated norbornene
ring-open polymer having a melting point of 110 to 145.degree.
C.
3. The hydrogenated norbornene ring-open polymer according to claim
2, having a weight average molecular weight (Mw) determined by gel
permeation chromatography (GPC) of 50,000 to 200,000.
4. The hydrogenated norbornene ring-open polymer according to claim
2, having a ratio (Mw/Mn) of the weight average molecular weight
(Mw) to the number average molecular weight (Mn) of 1.5 to
10.0.
5. A resin composition comprising the hydrogenated norbornene
ring-open polymer according to claim 1 or 2.
6. The resin composition according to claim 5, further comprising
0.01 to 1 part by weight of an antioxidant per 100 parts by weight
of the hydrogenated norbornene ring-open polymer.
7. A resin film or sheet obtained by molding the hydrogenated
norbornene ring-open polymer according to claim 1 or 2 or the resin
composition according to claim 5.
8. A molding material comprising a hydrogenated norbornene
ring-open polymer obtained by hydrogenating 80% or more of
carbon-carbon double bonds of a ring-open polymer which is obtained
by ring-opening polymerization of 2-norbornene or a
substituent-containing norbornene monomer, the proportion of a
repeating unit (A) derived from the 2-norbornene with respect to
all repeating units being 90 to 100 wt % and the proportion of a
repeating unit (B) derived from the substituent-containing
norbornene monomer with respect to all repeating units being 0 to
10 wt %, and the hydrogenated norbornene ring-open polymer having a
melting point of 110 to 145.degree. C., and the amount of organic
substances discharged from the molding material when heated at
80.degree. C. for 60 minutes being not more than 1 ppm.
9. The molding material according to claim 8, wherein the content
of transition metals is not more than 1 ppm.
10. A molded article obtained by molding the molding material
according to claim 8.
11. The molded article according to claim 10, which is a material
for processing electronic parts.
12. The molded article according to claim 11, which is a wafer
carrier for semiconductor production.
13. A multilayer laminate having two or more resin layers of which
at least one layer is a layer of a hydrogenated norbornene
ring-open polymer obtained by hydrogenating 80% or more of
carbon-carbon double bonds of a ring-open polymer which is obtained
by ring-opening polymerization of 2-norbornene or a monomer mixture
of 2-norbornene and a substituent-containing norbornene monomer,
the proportion of a repeating unit (A) derived from the
2-norbornene with respect to all repeating units being 90 to 100 wt
% and the proportion of a repeating unit (B) derived from the
substituent-containing norbornene monomer with respect to all
repeating units being 0 to 10 wt %, and the hydrogenated norbornene
ring-open polymer having a melting point of 110 to 145.degree.
C.
14. The multilayer laminate according to claim 13, wherein at least
one layer is a layer containing a gas barrier resin.
15. The multilayer laminate according to claim 14, wherein the gas
barrier resin is an ethylene-vinyl alcohol copolymer.
16. The multilayer laminate according to claim 13, wherein at least
one layer is a layer containing at least one resin selected from
the group consisting of a polyolefin resin, a polyamide resin, and
a polyester resin.
17. A packing material obtained by fabricating the multilayer
laminate according to claim 13.
18. A medical supply packing material having at least one resin
layer which is a layer of a hydrogenated norbornene ring-open
polymer obtained by hydrogenating 80% or more of carbon-carbon
double bonds of a ring-open polymer which is obtained by
ring-opening polymerization of 2-norbornene or a monomer mixture of
2-norbornene and a substituent-containing norbornene monomer, the
proportion of a repeating unit (A) derived from the 2-norbornene
with respect to all repeating units being 90 to 100 wt % and the
proportion of a repeating unit (B) derived from the
substituent-containing norbornene monomer with respect to all
repeating units being 0 to 10 wt %, and the hydrogenated norbornene
ring-open polymer having a melting point of 110 to 145.degree.
C.
19. The medical supply packing material according to claim 18,
further comprising at least one polyolefin resin layer.
20. The medical supply packing material according to claim 19,
wherein the polyolefin resin layer is a polyethylene resin
layer.
21. The medical supply packing material according to claim 18,
which is an infusion solution bag.
22. A blister molding sheet having at least one resin layer of a
hydrogenated norbornene ring-open polymer obtained by hydrogenating
80% or more of carbon-carbon double bonds of a ring-open polymer
which is obtained by ring-opening polymerization of 2-norbornene or
a monomer mixture of 2-norbornene and a substituent-containing
norbornene monomer, the proportion of a repeating unit (A) derived
from the 2-norbornene with respect to all repeating units being 90
to 100 wt % and the proportion of a repeating unit (B) derived from
the substituent-containing norbornene monomer with respect to all
repeating units being 0 to 10 wt %, and the hydrogenated norbornene
ring-open polymer having a melting point of 110 to 145.degree.
C.
23. The blister molding sheet according to claim 22, which is a
multilayer laminate comprising at least one polyolefin resin
layer.
24. The blister molding sheet according to claim 23, wherein the
polyolefin resin is a polypropylene resin.
25. A blister molded article obtained by molding the blister
molding sheet according to claim 22.
26. A blow-molded container having at least one resin layer of a
hydrogenated norbornene ring-open polymer obtained by hydrogenating
80% or more of carbon-carbon double bonds of a ring-open polymer
which is obtained by ring-opening polymerization of 2-norbornene or
a monomer mixture of 2-norbornene and a substituent-containing
norbornene monomer, the proportion of a repeating unit (A) derived
from the 2-norbornene with respect to all repeating units being 90
to 100 wt % and the proportion of a repeating unit (B) derived from
the substituent-containing norbornene monomer with respect to all
repeating units being 0 to 10 wt %, and the hydrogenated norbornene
ring-open polymer having a melting point of 110 to 145.degree. C.
Description
TECHNICAL FIELD
[0001] The present invention relates to a hydrogenated norbornene
ring-open polymer exhibiting excellent steam barrier properties,
heat resistance, oil resistance, mechanical properties,
processability, and the like which are properties demanded in
recent years in the fields of information processing, food
industries, medical supplies, engineering works, and the like, a
resin composition comprising the hydrogenated norbornene ring-open
polymer and an antioxidant, and a molded article obtained by
molding the hydrogenated norbornene ring-open polymer or the resin
composition.
BACKGROUND ART
[0002] Since a hydrogenated norbornene ring-open polymer has
excellent transparency and a low birefringence, application of the
polymer as a resin material for optical lenses or optical sheets
has been proposed (Patent Documents 1 and 2). In addition, since
the polymer exhibits excellent fluidity in a molten state and also
has excellent elusion properties and chemical resistance,
application of the polymer as a resin material for other than
optical application such as a packing film, a medical container,
and the like has been proposed (Patent Documents 3 and 4). However,
since many hydrogenated norbornene ring-open polymers are
amorphous, their moisture proofing properties, anti-sebum
properties, solvent resistance, and the like are insufficient.
Improvement of these properties has been desired.
[0003] As a hydrogenated norbornene ring-open polymer having
crystallinity (i.e. having a melting point), crystalline
hydrogenated products of a norbornene ring-open polymer containing
a repeating unit of norbornene monomers having 3 or more rings are
known (Patent Documents 5 to 7). Resin films or sheets obtained
from the hydrogenated norbornene ring-open polymers described in
these documents are excellent in transparency, heat resistance, and
chemical resistance, as well as mechanical strength. However, these
crystalline hydrogenated norbornene ring-open polymers have poor
solubility in solvents and deposit from the solvent after
hydrogenating the ring-open polymer, sometime making it difficult
to sufficiently purify the polymer by removing residual catalysts
and the like. In addition, the film molded from the hydrogenated
norbornene ring-open polymer did not fully satisfy the requirement
for moisture permeability.
[0004] Non-patent Documents 1 and 2 propose hydrogenated norbornene
ring-open polymers possessing a certain degree of crystallinity.
However, these documents do not specifically describe the
properties of the polymers. Among the specifically disclosed
polymers, those having a high molecular weight and a narrow
molecular weight distribution exhibited difficulty in controlling
the film thickness when the film is produced. Films made from the
polymer having a small molecular weight had a small tensile
breaking elongation, indicating that the polymer has a problem of
mechanical properties when made into a film. Furthermore, since the
hydrogenation degree is not necessarily enough, molded products
made from the polymer are easily burned.
[0005] Along with high integration of semiconductor chips and
liquid crystal display devices in the electronic fields, quality
degradation due to mixing of contaminants such as fine particles,
moisture, and organic substances during the manufacturing process
poses a serious problem. Therefore, it is necessary to store and
transport precision substrates such as a silicon wafer substrate, a
liquid crystal display substrate, and the like used for production
of these parts under an environment where the above-mentioned
contaminants are reduced to an amount as small as possible. For
this reason, a method of storing and transporting these precision
substrates in a state isolated from the outside environment by
utilizing an airtight container of which the inside is highly
purified (a wafer carrier for semiconductor production) is
used.
[0006] A method of filling the container with clean air or an inert
gas in order to prevent contaminants such as fine particles from
adhering to the precision substrate stored in the container has
also been employed. In order to respond to the recent demand for
further low contamination, a method of evacuating the internal
atmosphere of the container to provide vacuum or reduced pressure
conditions has been proposed. The container of which the internal
atmosphere is evacuated not only must be airtight and pressure
resistant, but also the container material itself must not
discharge contaminants such as moisture and organic substances.
[0007] As a container satisfying these requirements, a metal
container and a container made from a thermoplastic resin having
excellent chemical resistance and low water absorptivity such as
polypropylene (PP), polytetrafluoroethylene (PTFE), perfluoroalkoxy
fluororesin (PFA), or the like are known.
[0008] However, a metal container is heavy, cannot allow
observation of the precision substrates stored therein, and has a
high manufacturing cost. PP is opaque and has poor dimensional
accuracy and heat resistance. PTFE is not only opaque and has poor
dimensional accuracy, but also does not allow injection molding,
making mass production difficult. The PTFE product is therefore
expensive. PFA has insufficient transparency and poor dimensional
accuracy, and it is difficult to synthesize PFA and to manufacture
the product in a large scale. The PFA product is thus also
expensive.
[0009] As a molding material which solves these problems, a
thermoplastic norbornene resin which can be molded by injection
molding and has excellent heat resistance, moisture resistance,
chemical resistance, transparency, and the like is attracting
attention in recent years.
[0010] For example, a thermoplastic resin container formed from a
cycloolefin resin is proposed in Patent Document 8. The Patent
Document 8 describes that a hydrogenated norbornene ring-open
polymer is preferable as a cycloolefin resin due to the small
content of impurities such as low molecular weight components,
catalyst residues, metals, and the like in the resin and also due
to high transparency.
[0011] Patent Document 9 proposes a material for producing
semiconductors formed from a thermoplastic saturated norbornene
resin having a contact surface of 18.6 kgf/cm.sup.2 at a load
deflecting temperature of 70.degree. C. Patent Document 10 proposes
a container for precision substrates made from a thermoplastic
resin and having one or more components which have specific
properties. A hydrogenated norbornene ring-open polymer and the
like are given as a preferable thermoplastic resin.
[0012] However, when a wafer carrier for semiconductor production
is fabricated using the thermoplastic resin molding material
described in these Patent Documents, there is a problem that the
surface of the semiconductors in the carrier is contaminated with
an organic substance discharged from the molded article. In
addition, when the wafer is inserted into or removed from the
carrier, the carrier may be caused to come into contact with the
wafer and produce a resin powder (foreign matter) which
contaminates the wafer.
[0013] In the field of medical supplies and food packing, packing
materials for medical supplies such as an infusion solution bag, a
blood bag, a bottle for medicine, a cell used for analysis, and a
medical test tube, as well as packing materials for food such as
bean paste, soy sauce, and mayonnaise are widely used. These
packing materials are required to possess transparency, chemical
resistance, impact resistance, capability of being repeatedly
sterilized, steam barrier properties, and the like. In order to
satisfy these requirements, a number of packing materials for
medical supplies and foods using a synthetic resin such as a
thermoplastic norbornene resin having excellent transparency or
chemical resistance have been proposed.
[0014] For example, Patent Document 11 proposes a packing container
for medical supplies and foods of which the wall is made of a
multilayer laminate, at least one layer being made of a
thermoplastic norbornene polymer.
[0015] Patent Document 12 discloses a molded article prepared by
laminating a gas barrier resin layer of a partially saponified
polyvinyl acetate on the surface of a thermoplastic norbornene
resin molded article.
[0016] However, all the thermoplastic norbornene resins described
in these Documents are amorphous materials which have insufficient
impact resistance and oil resistance when used as a packing
material for medical supplies. Moreover, the packing container for
medical supplies and foods described in Patent Document 11 has poor
steam barrier properties. The molded article described in Patent
Document 12, in which thermoplastic norbornene resin has poor steam
barrier properties, has a problem of degradation of oxygen barrier
properties due to denaturing of the gas barrier resin layer by
water in a high temperature and high humidity environment.
[0017] On the other hand, Patent Document 13 proposes a film or a
sheet obtained by molding a norbornene ring-open polymer having a
melting point or a hydrogenated norbornene ring-open polymer having
a melting point obtained by hydrogenating the carbon-carbon double
bonds in the ring-open polymer.
[0018] However, the hydrogenated dicyclopentadiene ring-open
polymer having a melting point which is specifically disclosed in
this Patent Document can be molded only with difficulty due to
unduly high melting point of 270.degree. C. or more. In addition,
the resulting molded product has poor steam barrier properties and
mechanical properties such as impact resistance.
[0019] Blister molded articles such as a press-through package
(PTP) have been manufactured by producing a resin sheet (sheet for
blister mold) and molding the sheet by a heat molding method such
as vacuum molding or pressure molding.
[0020] Outstanding moldability, damp proofing (steam barrier)
properties, impact resistance, oil resistance, and the like are
required for such blister molded articles. In order to satisfy
these requirements, a number of blister molded articles made of a
synthetic resin such as a thermoplastic norbornene resin have been
proposed.
[0021] For example, Patent Document 14 discloses a press through
package (PTP) with a packed material contained therein. The package
is prepared by enclosing the material to be packed in a pocket
provided on a sheet of a thermoplastic norbornene resin and
blocking the pocket opening of the sheet with another sheet.
[0022] Patent Document 15 discloses a multilayer sheet for packing
drugs requiring high moisture proofing properties. The sheet is
made from (A) an amorphous polyolefin having a heat distortion
temperature of 100.degree. C. or less, which is a copolymer of a
product of the Diels-Alder addition reaction of cyclopentadiene (or
a derivative thereof) and norbornadiene (or a derivative thereof)
and an unsaturated monomer and (B) polypropylene, wherein a layer
of the polypropylene (B) is laminated on at least one side of the
amorphous polyolefin resin layer (A).
[0023] However, all thermoplastic norbornene resins described in
these Documents are amorphous resins, which may sometimes have
insufficient mechanical strength, heat resistance, and oil
resistance when used as a blister molded article. The PTP described
in Patent Document 14 may become whitened by adhesion of sebum
during use, and the high moisture proofing multilayer sheet for
packing drugs described in Patent Document 15 has a problem of poor
steam barrier properties.
[0024] In order to obviate these problems, Patent Document 16
proposes a film or a sheet formed from a norbornene ring-open
polymer having a melting point or a hydrogenated norbornene
ring-open polymer having a melting point obtained by hydrogenating
the carbon-carbon double bonds in the ring-open polymer.
[0025] However, the hydrogenated dicyclopentadiene ring-open
polymer having a melting point which is specifically disclosed in
this Patent Document can be molded only with difficulty due to
unduly high melting point of 270.degree. C. or more. In addition,
the resulting molded product may have poor steam barrier properties
and mechanical properties.
[0026] On the other hand, Patent Document 17 discloses a
blow-molded article prepared by blow molding of a norbornene
polymer having a melting point. The norbornene polymer having a
melting point described in Patent Document 17 is a crystalline
polymer. Various hydrogenated ring-open polymers of norbornene
monomers are mentioned as the norbornene polymer having a melting
point in Patent Document 17. However, the Document specifically
describes only a hydrogenated ring-open polymer of
dicyclopentadiene. The hydrogenated dicyclopentadiene ring-open
polymer is a polymer having a high melting point of 200 to
400.degree. C.
[0027] Therefore, in the blow molding process shown in examples of
Patent Document 17, the hydrogenated dicyclopentadiene ring-open
polymer is extruded from a biaxial extruder at a barrel temperature
of 290 to 300.degree. C. and a die temperature of about 320.degree.
C. to produce a molten parison. Molding at such a high temperature
not only subjects the molding machine to a significant load, but
also tends to produce resin burning (discoloration). Although the
resulting blow-molded container is excellent in heat resistance,
oil resistance, chemical resistance, and the like, the steam
barrier properties are not necessarily sufficient. In addition,
since the hydrogenated dicyclopentadiene ring-open polymer can be
dissolved in an organic solvent only with difficulty, purification
of the product is difficult and the product has a problem of
elution of metals derived from the catalyst.
[0028] The above-mentioned Non-patent Document 1 reports that a
crystalline thermoplastic polymer with a melting point of
141.degree. C. was obtained by hydrogenating an amorphous
polynorbornene having a trans content of 80% and a weight average
molecular weight (Mw) of 2,000,000.
[0029] Non-patent Document 2 reports the crystal structure and
melting point of a block copolymer of hydrogenated polynorbornene
and hydrogenated polyethylidene norbornene (hPN/hPEN).
[0030] However, since the hydrogenated norbornene ring-open
polymers disclosed by Non-patent Documents 1 and 2 have a large
number average molecular weight (Mn) and a narrow molecular weight
distribution (Mw/Mn), it is difficult to precisely control the
thickness of the container formed if the polymers are molded by
blow molding. In fact, neither Non-patent Document 1 nor Non-patent
Document 2 describes production of a molded article by blow molding
of the hydrogenated polymers. [0031] [Patent Document 1]
JP-A-60-26024 [0032] [Patent Document 2] JP-A-9-263627 [0033]
[Patent Document 3] JP-A-2000-313090 [0034] [Patent Document 4]
JP-A-2003-183361 [0035] [Patent Document 5] JP-A-2000-201826 [0036]
[Patent Document 6] JP-A-2000-393316 [0037] [Patent Document 7]
JP-A-2006-52333 [0038] [Patent Document 8] JP-A-11-74337 [0039]
[Patent Document 9] JP-A-2002-217279 [0040] [Patent Document 10] WO
2003/021665 [0041] [Patent Document 11] JP-A-4-276253 [0042]
[Patent Document 12] JP-A-2002-127315 [0043] [Patent Document 13]
JP-A-2002-194067 [0044] [Patent Document 14] JP-A-6-278706 [0045]
[Patent Document 15] JP-A-7-178884 [0046] [Patent Document 16]
JP-A-2002-194067 [0047] [Patent Document 17] JP-A-2002-249554
[0048] [Non-patent Document 1] Polymer International, Vol. 34, pp.
49-57 (1994) [0049] [Non-patent Document 2] Macromolecules, Vol.
37, pp. 7278-7284 (2004)
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0050] The present invention has been achieved in view of this
situation in general technology and has an object of providing the
following (a) to (g):
(a) a hydrogenated norbornene ring-open polymer which can be used
as a resin material exhibiting excellent steam barrier properties,
heat resistance, oil resistance, mechanical properties,
processability, and the like which are properties demanded in
recent years in the fields of information processing, food
industries, medical supplies, engineering works, and the like in
recent years, and a resin composition comprising the hydrogenated
norbornene ring-open polymer, (b) a resin film or sheet obtainable
by molding the above hydrogenated norbornene ring-open polymer or
resin composition, (c) a molded article useful as a material for
processing electronic parts obtainable by molding the above
hydrogenated norbornene ring-open polymer or resin composition, (d)
a multilayer laminate having excellent damp proofing (steam
barrier) properties, mechanical properties such as impact
resistance, and oil resistance, as well as excellent gas barrier
properties in a high temperature and high humidity environment
(when the multilayer laminate includes at least one layer
containing a gas barrier resin), and a packing material obtained by
fabricating the multilayer laminate, (e) a medical supply packing
material having steam barrier properties, mechanical properties,
oil resistance, pliability, and moldability, and particularly
excellent steam barrier properties at a high temperature, (f) a
blister molding sheet having excellent steam barrier properties,
oil resistance, and processability, particularly having excellent
steam barrier properties at a high temperature, and a
blister-molded article obtained by molding the blister molding
sheet, and (g) a monolayer or multilayer blow-molded container,
each layer containing a hydrogenated norbornene ring-open polymer,
having excellent steam barrier properties, heat resistance, oil
resistance, mechanical properties, processability, and the like,
and having a small haze.
[0051] In order to achieve the above object, a first aspect of the
present invention provides a hydrogenated norbornene ring-open
polymer, a resin composition, a resin sheet, a resin film, and a
sheet described in (1) to (7) below.
(1) A hydrogenated norbornene ring-open polymer obtained by
hydrogenating 80% or more of main-chain carbon-carbon double bonds
of a ring-open polymer which is obtained by ring-opening
polymerization of 2-norbornene, the hydrogenated norbornene
ring-open polymer having a weight average molecular weight (Mw)
determined by gel permeation chromatography (GPC) of 50,000 to
200,000, a molecular weight distribution (Mw/Mn) of 1.5 to 10.0,
and a melting point of 110 to 145.degree. C. (2) A hydrogenated
norbornene ring-open polymer obtained by hydrogenating 80% or more
of carbon-carbon double bonds of a ring-open polymer which is
obtained by ring-opening copolymerization of 2-norbornene and a
substituent-containing norbornene monomer, the proportion of a
repeating unit (A) derived from the 2-norbornene with respect to
all repeating units being 90 to 99 wt % and the proportion of a
repeating unit (B) derived from the substituent-containing
norbornene monomer with respect to all repeating units being 1 to
10 wt %, and the hydrogenated norbornene ring-open polymer having a
melting point of 110 to 145.degree. C. (3) The hydrogenated
norbornene ring-open polymer according to (2), having a weight
average molecular weight (Mw) determined by gel permeation
chromatography (GPC) of 50,000 to 200,000. (4) The hydrogenated
norbornene ring-open polymer according to (2), having a ratio
(Mw/Mn) of the weight average molecular weight (Mw) to the number
average molecular weight (Mn) of 1.5 to 10.0. (5) A resin
composition comprising the hydrogenated norbornene ring-open
polymer of (1) or (2). (6) The resin composition according to (5),
further comprising 0.01 to 1 part by weight of an antioxidant per
100 parts by weight of the hydrogenated norbornene ring-open
polymer. (7) A resin film or sheet obtained by molding the
hydrogenated norbornene ring-open polymer described in (1) or (2)
or the resin composition described in (5).
[0052] According to a second aspect of the present invention,
molding materials and molded articles described in (8) to (12)
below are provided.
(8) A molding material comprising a hydrogenated norbornene
ring-open polymer obtained by hydrogenating 80% or more of
carbon-carbon double bonds of a ring-open polymer which is obtained
by ring-opening polymerization of 2-norbornene or a
substituent-containing norbornene monomer, the proportion of a
repeating unit (A) derived from the 2-norbornene with respect to
all repeating units being 90 to 100 wt % and the proportion of a
repeating unit (B) derived from the substituent-containing
norbornene monomer with respect to all repeating units being 0 to
10 wt %, and the hydrogenated norbornene ring-open polymer having a
melting point of 110 to 145.degree. C., and the amount of organic
substances discharged from the molding material when heated at
80.degree. C. for 60 minutes being not more than 1 ppm. (9) The
molding material according to (8), wherein the content of
transition metals is not more than 1 ppm. (10) A molded article
obtained by molding the molding material according to (8). (11) The
molded article according to (10), which is a material for
processing electronic parts. (12) The molded article according to
(11), which is a wafer carrier for semiconductor production.
[0053] According to a third aspect of the present invention,
multilayer laminates and packing materials described in (13) to
(17) below are provided.
(13) A multilayer laminate having two or more resin layers of which
at least one layer is a layer of a hydrogenated norbornene
ring-open polymer obtained by hydrogenating 80% or more of
carbon-carbon double bonds of a ring-open polymer which is obtained
by ring-opening polymerization of 2-norbornene or a monomer mixture
of 2-norbornene and a substituent-containing norbornene monomer,
the proportion of a repeating unit (A) derived from the
2-norbornene with respect to all repeating units being 90 to 100 wt
% and the proportion of a repeating unit (B) derived from the
substituent-containing norbornene monomer with respect to all
repeating units being 0 to 10 wt %, and the hydrogenated norbornene
ring-open polymer having a melting point of 110 to 145.degree. C.
(14) The multilayer laminate according to (13), wherein at least
one layer is a layer containing a gas barrier resin. (15) The multi
layer laminate according to (13), wherein the gas barrier resin is
an ethylene-vinyl alcohol copolymer. (16) The multi layer laminate
according to (13), wherein at least one layer is a layer containing
at least one resin selected from the group consisting of a
polyolefin resin, a polyamide resin, and a polyester resin. (17) A
packing material obtained by fabricating the multilayer laminate
according to (13).
[0054] According to a fourth aspect of the present invention, a
medical supply packing material described in (18) to (21) below is
provided.
(18) A medical supply packing material having at least one resin
layer which is a layer of a hydrogenated norbornene ring-open
polymer obtained by hydrogenating 80% or more of carbon-carbon
double bonds of a ring-open polymer which is obtained by
ring-opening polymerization of 2-norbornene or a monomer mixture of
2-norbornene and a substituent-containing norbornene monomer, the
proportion of a repeating unit (A) derived from the 2-norbornene
with respect to all repeating units being 90 to 100 wt % and the
proportion of a repeating unit (B) derived from the
substituent-containing norbornene monomer with respect to all
repeating units being 0 to 10 wt %, and the hydrogenated norbornene
ring-open polymer having a melting point of 110 to 145.degree. C.
(19) The medical supply packing material according to (18), further
comprising at least one polyolefin resin layer. (20) The medical
supply packing material according to (19), wherein the polyolefin
resin layer is a polyethylene resin layer. (21) The medical supply
packing material according to (18), which is an infusion solution
bag.
[0055] According to a fifth aspect of the present invention, a
blister molding sheet and a blister molded article described in
(22) to (25) below are provided.
(22) A blister molding sheet having at least one resin layer of a
hydrogenated norbornene ring-open polymer obtained by hydrogenating
80% or more of carbon-carbon double bonds of a ring-open polymer
which is obtained by ring-opening polymerization of 2-norbornene or
a monomer mixture of 2-norbornene and a substituent-containing
norbornene monomer, the proportion of a repeating unit (A) derived
from the 2-norbornene with respect to all repeating units being 90
to 100 wt % and the proportion of a repeating unit (B) derived from
the substituent-containing norbornene monomer with respect to all
repeating units being 0 to 10 wt %, and the hydrogenated norbornene
ring-open polymer having a melting point of 110 to 145.degree. C.
(23) The blister molding sheet according to (22), which is a
multilayer laminate comprising at least one polyolefin resin layer.
(24) The blister molding sheet according to (23), wherein the
polyolefin resin is a polypropylene resin. (25) A blister molded
article obtained by molding the blister molding sheet according to
(22).
[0056] According to a sixth aspect of the present invention, a
blow-molded container described in (26) below is provided.
(26) A blow-molded container having at least one resin layer of a
hydrogenated norbornene ring-open polymer obtained by hydrogenating
80% or more of carbon-carbon double bonds of a ring-open polymer
which is obtained by ring-opening polymerization of 2-norbornene or
a monomer mixture of 2-norbornene and a substituent-containing
norbornene monomer, the proportion of a repeating unit (A) derived
from the 2-norbornene with respect to all repeating units being 90
to 100 wt % and the proportion of a repeating unit (B) derived from
the substituent-containing norbornene monomer with respect to all
repeating units being 0 to 10 wt %, and the hydrogenated norbornene
ring-open polymer having a melting point of 110 to 145.degree.
C.
Effect of the Invention
[0057] According to the present invention, a hydrogenated
norbornene ring-open polymer which can be used as a resin material
exhibiting excellent steam barrier properties, heat resistance, oil
resistance; mechanical properties, processability, and the like
which are properties demanded in recent years in the fields of
information, food industries, medical supplies, engineering works,
and the like, a resin composition comprising the hydrogenated
norbornene ring-open polymer, and a resin film or resin sheet
obtained by molding the resin composition can be obtained.
[0058] According to the present invention, a molding material
having excellent heat resistance, discharging only a minimal amount
of organic compounds, and generating only a very slight amount of
foreign matters by friction from a molded article, as well as a
molded article obtained by molding the molding material can be
provided.
[0059] The multilayer laminate and the packing material of the
present invention have excellent steam barrier properties,
mechanical properties such as impact resistance, and oil
resistance, and when possessing at least one layer containing a gas
barrier resin, have excellent gas barrier properties in a high
temperature and high humidity environment.
[0060] The medical supply packing material of the present invention
has excellent steam barrier properties, mechanical properties, oil
resistance, pliability, and moldability. The medical supply packing
material particularly exhibits superior steam barrier properties at
a high temperature.
[0061] The blister molding sheet and the blister-molded article of
the present invention have excellent steam barrier properties, oil
resistance, and processability. The steam barrier properties of the
blister molding sheet and the blister-molded article at a high
temperature is particularly excellent.
[0062] According to the present invention, a monolayer or
multilayer blow-molded container, each layer containing a
hydrogenated norbornene ring-open polymer, having excellent steam
barrier properties, heat resistance, oil resistance, mechanical
properties, processability, and the like, and having a small haze
can be provided.
BRIEF DESCRIPTION OF THE DRAWING
[0063] FIG. 1 is a perspective diagram of a wafer carrier for
producing a semiconductor according to the present invention.
BEST MODE FOR CARRYING OUT THE INVENTION
[0064] The present invention will be described in detail below.
1) Hydrogenated Norbornene Ring-Open Polymer
[0065] The hydrogenated norbornene ring-open polymer of the present
invention is a polymer described in either (I) or (II) below.
(I) A hydrogenated norbornene ring-open polymer obtained by
hydrogenating 80% or more of main-chain carbon-carbon double bonds
of a ring-open polymer which is obtained by ring-opening
polymerization of 2-norbornene (hydrogenated 2-norbornene ring-open
polymer), the hydrogenated 2-norbornene ring-open polymer having a
weight average molecular weight (Mw) determined by gel permeation
chromatography (GPC) of 50,000 to 200,000, a molecular weight
distribution (Mw/Mn) of 1.5 to 10, and a melting point of 110 to
145.degree. C. (hereinafter may be referred to from time to time as
"hydrogenated norbornene ring-open polymer (I)"). (II) A
hydrogenated norbornene ring-open polymer obtained by hydrogenating
80% or more of carbon-carbon double bonds of a ring-open polymer
which is obtained by ring-opening polymerization of 2-norbornene
and a substituent-containing norbornene monomer, the proportion of
a repeating unit (A) derived from the 2-norbornene with respect to
all repeating units being 90 to 99 wt % and the proportion of a
repeating unit (B) derived from the substituent-containing
norbornene monomer with respect to all repeating units being 1 to
10 wt %, and the hydrogenated norbornene ring-open polymer having a
melting point of 110 to 145.degree. C. (hereinafter may be referred
to from time to time as "hydrogenated norbornene ring-open polymer
(II)").
[0066] The proportion of the repeating unit (A) derived from
2-norbornene with respect to all repeating units in the
hydrogenated norbornene ring-open polymer (II) of the present
invention is 90 to 99 wt %, preferably 95 to 99 wt %, and more
preferably 97 to 99 wt %. The proportion of the repeating unit (B)
derived from substituent-containing norbornene monomer with respect
to all repeating units is 1 to 10 wt %, preferably 1 to 5 wt %, and
more preferably 1 to 3 wt %.
[0067] If the proportion of the repeating unit (A) and the
repeating unit (B) is in this range, the hydrogenated norbornene
ring-open polymer has good solubility in solvents. Therefore, the
polymer can be obtained with excellent productivity and can be
purified with ease. In addition, the resulting molded article may
have good mechanical properties, transparency, heat resistance, and
steam barrier properties. Furthermore, the resin discharges only a
very small amount of organic substances and generates resin powder
(foreign matter) by friction and the like only with difficulty.
[0068] If the amount of the repeating unit (B) is too large, the
heat resistance and steam barrier properties of the molded article
may be impaired. In addition, the amount of organic substances
discharged from the resin may increase and the molded article tends
to easily generate resin powder (foreign matter) by friction.
[0069] If the amount of the repeating unit (B) is too small, the
solubility of the hydrogenated polymer in solvents decreases,
resulting in poor productivity of the polymer and difficulty in
polymer purification. In addition, the mechanical properties of the
molded article may be impaired. Moreover, the resulting molded
article may more easily generate resin powder (foreign matter) by
friction.
[0070] 2-Norbornene used in the present invention is a known
compound. This compound may be obtained by reacting cyclopentadiene
and ethylene, for example. Industrially available 2-norbornene
usually contains impurities.
[0071] As examples of the impurities, cyclopentadiene, norbornane,
methylnorbornene, dimethyldicyclopentadiene, and the like can be
given. Of these, methylnorbornene, dimethylcyclopentadiene, and the
like are monomers copolymerizable with 2-norbornene by ring-opening
copolymerization.
[0072] The impurities in 2-norbornene is usually less than 1 wt %,
preferably less than 0.8 wt %, and more preferably less than 0.5 wt
%. The heat resistance of the hydrogenated norbornene ring-open
polymer is maintained at a high level when the content of
impurities is within this range.
[0073] Since the 2-norbornene used may contain other monomers
copolymerizable with 2-norbornene by ring-opening copolymerization
as mentioned above, the hydrogenated norbornene ring-open polymer
(I) also contains a ring-open copolymer which contains a small
amount of other monomers copolymerizable with 2-norbornene by
ring-opening copolymerization. The amount of the monomers
copolymerizable with 2-norbornene in the polymer is usually not
more than 1 wt %, preferably not more than 0.8 wt %, and more
preferably not more than 0.5 wt %.
[0074] The substituent-containing norbornene monomer used in the
present invention is a compound which has a norbornene skeleton in
the molecule (excluding 2-norbornene).
[0075] The term "substituent-containing norbornene monomer" used in
the present invention includes norbornene compounds possessing a
condensed ring, in addition to 2-norbornene derivatives having a
substituent.
[0076] As the substituent-containing norbornene monomer, a
norbornene monomer not containing a ring condensable with a
norbornene ring in the molecule, a polycyclic norbornene monomer
having three or more rings, and the like can be given.
[0077] As examples of the norbornene monomer not containing a ring
condensable with a norbornene ring in the molecule, norbornenes
having an alkyl group such as 5-methylnorbornene,
5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene,
5-decylnorbornene, 5-cyclohexylnorbornene, and
5-cyclopentylnorbornene; norbornenes having an alkenyl group such
as 5-ethylidenenorbornene, 5-vinylnorbornene, 5-propenylnorbornene,
5-cyclohexenylnorbornene, and 5-cyclopentenylnorbornene;
norbornenes having an aromatic ring such as 5-phenylnorbornene;
norbornenes having a polar group containing an oxygen atom such as
5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene,
5-methyl-5-methoxycarbonylnorbornene,
5-methyl-5-ethoxycarbonylnorbornene,
norbornenyl-2-methylpropionate, norbornenyl-2-methyloctanate,
5-hydroxymethylnorbornene, 5,6-di(hydroxymethyl)norbornene,
5,5-di(hydroxymethyl)norbornene, 5-hydroxy-1-propylnorbornene,
5,6-dicarboxynorbornene, and 5-methoxycarbonyl-6-carboxynorbornene;
norbornenes having a polar group containing a nitrogen atom such as
5-cyanonorbornene; and the like can be given.
[0078] The polycyclic norbornene monomer having three or more rings
is to a norbornene monomer having a norbornene ring and one or more
rings condensed with the norbornene ring in the molecule. As
specific examples, monomers shown by the following formulas (2) and
(3) can be given.
##STR00001##
wherein R.sup.1 and R.sup.2 individually represent a hydrogen atom,
a halogen atom, a substituted or unsubstituted hydrocarbon group
having 1 to 20 carbon atoms, or a substituent containing a silicon
atom, an oxygen atom, or a nitrogen atom, R.sup.1 and R.sup.2 may
bond together to form a ring, and R.sup.3 represents a substituted
or unsubstituted divalent hydrocarbon group having 1 to 20 carbon
atoms.
##STR00002##
wherein R.sup.4 to R.sup.7 individually represent a hydrogen atom,
a halogen atom, a substituted or unsubstituted hydrocarbon group
having 1 to 20 carbon atoms, or a substituent containing a silicon
atom, an oxygen atom or a nitrogen atom, wherein R.sup.4 and
R.sup.6 may bond together to form a ring, and m is an integer of 1
or 2.
[0079] As specific examples of the monomer shown by the above
formula (2), dicyclopentadiene, methyldicyclopentadiene,
dimethyldicyclopentadiene, and tricyclo[5.2.1.0.sup.2,6]dec-8-ene
can be given. Norbornene derivatives having an aromatic ring such
as
tetracyclo[9.2.1.0.sup.2,10.0.sup.3,8]tetradeca-3,5,7,12-tetraene
(also called 1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene) and
tetracyclo[10.2.1.0.sup.2,11.0.sup.4,9]pentadeca-4,6,8,13-tetraene
(also called 1,4-methano-1,4,4a,9,9a,10-hexahydroanthracene) can
also be given.
[0080] As examples of the monomer shown by the above formula (3),
tetracyclododecenes which are the compounds of the formula (3) in
which m=1 and hexacycloheptadecenes which are compounds of the
formula (3) in which m=2 can be given.
[0081] As specific examples of tetracyclododecenes,
tetracyclododecenes unsubstituted or substituted with an alkyl
group such as tetracyclododecene, 8-methyltetracyclododecene,
8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and
8-cyclopentyltetracyclododecene; tetracyclododecenes having a
double bond outside of the ring such as 8-methyl
idenetetracyclododecene, 8-ethylidenetetracyclododecene,
8-vinyltetracyclododecene, 8-propenyltetracyclododecene,
8-cyclohexenyltetracyclododecene, and
8-cyclopentenyltetracyclododecene; tetracyclododecenes having an
aromatic ring such as 8-phenyltetracyclododecene;
tetracyclododecenes having an oxygen-containing substituent such as
8-methoxycarbonyltetracyclododecene,
8-methyl-8-methoxycarbonyltetracyclododecene,
8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene,
tetracyclododecene-8,9-dicarboxylic acid, and
tetracyclododecene-8,9-dicarboxylic anhydride; tetracyclododecenes
having a nitrogen-containing substituent such as
8-cyanotetracyclododecene and tetracyclododecene-8,9-dicarboxylic
acid imide; tetracyclododecenes having a halogen-containing
substituent such as 8-chlorotetracyclododecene; and
tetracyclododecenes having a silicon-containing substituent such as
8-trimethoxysilyltetracyclododecene can be given.
[0082] As specific examples of hexacycloheptadecenes,
hexacycloheptadecenes unsubstituted or substituted with an alkyl
group such as hexacycloheptadecene, 12-methylhexacycloheptadecene,
12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene,
and 12-cyclopentylhexacycloheptadecene; hexacycloheptadecenes
having a double bond outside of the ring such as
12-methylidenehexacycloheptadecene,
12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene,
12-propenylhexacycloheptadecene,
12-cyclohexenylhexacycloheptadecene, and
12-cyclopentenylhexacycloheptadecene; hexacycloheptadecenes having
an aromatic ring such as 12-phenylhexacycloheptadecene;
hexacycloheptadecenes having an oxygen-containing substituent such
as 12-methoxycarbonylhexacycloheptadecene,
12-methyl-12-methoxycarbonylhexacycloheptadecene,
12-hydroxymethylhexacycloheptadecene,
12-carboxyhexacycloheptadecene,
hexacycloheptadecene-12,13-dicarboxylic acid, and
hexacycloheptadecene-12,13-dicarboxylic anhydride;
hexacycloheptadecenes having a nitrogen-containing substituent such
as 12-cyanohexacycloheptadecene and
hexacycloheptadecene-12,13-dicarboxylic acid imide;
hexacycloheptadecenes having a halogen-containing substituent such
as 12-chlorohexacycloheptadecene; and hexacycloheptadecenes having
a silicon-containing substituent such as
12-trimethoxysilylhexacycloheptadecene can be given. These
norbornene monomers may be used either individually or in
combination of two or more.
[0083] In the case of providing the hydrogenated norbornene
ring-open polymer (II), other monomers copolymerizable with the
2-norbornene and substituent-containing norbornene monomers may be
used in combination.
[0084] As examples of the other monomer copolymerizable with
2-norbornene monomer and substituent-containing norbornene
monomers, monocyclic olefins such as cyclohexene, cycloheptene, and
cyclooctene, and derivatives thereof; cyclic diener such as
cyclohexadiene and cycloheptadiene, and derivatives thereof; and
the like can be given.
(Ring-Opening Polymerization)
[0085] The ring-opening polymerization of 2-norbornene or the
ring-opening copolymerization of 2-norbornene and a
substituent-containing norbornene monomer may be carried out in the
presence of a metathesis polymerization catalyst in a solvent or
without using a solvent.
[0086] As the metathesis polymerization catalyst, a general
metathesis polymerization catalyst which essentially consists of
(a) a transition metal compound catalyst component and (b) a
metallic compound co-catalyst component described in JP-B-41-20111,
JP-A-46-14910, JP-B-57-17883, JP-B-57-61044, JP-A-54-86600,
JP-A-58-127728, and JP-A-1-240517; a living ring-opening metathesis
catalyst such as Schrock-type polymerization catalyst
(JP-A-7-179575, Schrock et al., J. Am. Chem. Soc., 1990, vol. 112,
from page 3875), Grubbs polymerization catalyst (Fu et al., J. Am.
Chem. Soc., 1993, Vol. 115, from page 9856), Nguyen et al., J. Am.
Chem. Soc., 1992, vol 114, from page 3974; Grubbs et al. WO
98/21214, etc.); and the like can be given.
[0087] Taking the molecular weight distribution of the polymer into
consideration, a metathesis polymerization catalyst comprising
(.alpha.) a transition metal compound catalyst component and
(.beta.) a metallic compound co-catalyst component is preferable
among these catalysts.
[0088] The transition metal compound catalyst components (.alpha.)
are transition metal compounds of the groups 3 to 11 of the
Periodic Table. As examples of the specific transition metal
compound, a halide, an oxyhalide, an alkoxyhalide, an alkoxide, a
carbonate, an (oxy)acetylacetonate, a carbonyl complex, an
acetonitrile complex, and an hydride complex of these transition
metals, derivatives of these compounds, and complex compounds of
these, which are obtained by a complexing agent such as
P(C.sub.6H.sub.5).sub.5 and the like can be given.
[0089] As specific examples, TiCl.sub.4, TiBr.sub.4, VOCl.sub.3,
WBr.sub.3, WCl.sub.6, WOCl.sub.4, MoCl.sub.5, MoOCl.sub.4,
WO.sub.2, and H.sub.2WO.sub.4 can be given. Among these compounds,
compounds of W, Mo, Ti, or V, particularly a halide, an oxyhalide,
or an alkoxyhalide are preferable from the viewpoint of
polymerization activity.
[0090] The metallic compound co-catalyst component (.beta.) is a
compound having at least one metal element-carbon atom bond or at
least one metal element-hydrogen bond of a metal belonging to the
groups 1 to 2 and the groups 12 to 14 of the Periodic Table. For
example, an organic compound of Al, Sn, Li, Na, Mg, Zn, Cd, and B
can be given.
[0091] As specific examples, organoaluminum compounds such as
trimethylaluminum, triisobutylaluminum, diethylaluminum
monochloride, methylaluminum sesquichloride, and ethylaluminum
dichloride; organotin compounds such as tetramethyltin,
diethyldimethyltin, tetrabutyltin, and tetraphenyltin;
organiolithium compounds such as n-butyllithium; organosodium
compounds such as n-pentylsodium; organomagnesium compounds such as
methylmagnesium iodide; organozinc compounds such as diethylzinc;
organocadmium compounds such as diethyl cadmium; and organoboron
compounds such as trimethylboron can be given. Of these, compounds
of elements belonging to the group 13, particularly organoaluminum
compounds of Al, are preferable.
[0092] It is possible to increase the metathesis polymerization
activity by adding a third component in addition to the component
(.alpha.) and the component (.beta.). Examples of the third
component used include aliphatic tertiary amines, aromatic tertiary
amines, molecular oxygen, alcohols, ethers, peroxides, carboxylic
acids, acid anhydrides, acid chlorides, esters, ketones,
nitrogen-containing compounds, halogen-containing compounds, and
other Lewis acids.
[0093] The ratio of the component (.alpha.) to the component
(.beta.), in terms of molar ratio of metals, is usually in a range
of 1:1 to 1:100, and preferably 1:2 to 1:10. The molar ratio of the
component (.alpha.) to the third component is usually in a range of
1:0.005 to 1:50, and preferably 1:1 to 1:10.
[0094] The amount of the polymerization catalyst used, in terms of
molar ratio of the transition metals in the polymerization catalyst
to the total amount of monomers, is usually 1:100 to 1:2,000,000,
preferably 1:1,000 to 1:20,000, and more preferably 1:5,000 to
1:8,000. If the amount of the catalyst is too large, the catalyst
removal after the polymerization reaction will become difficult and
there is a possibility that the molecular weight distribution may
be broadened. If too small, sufficient polymerization activity may
not be obtained.
[0095] It is preferable to carry out in the ring-opening
polymerization in an appropriate solvent, although a non-solvent
reaction is possible. There are no specific limitations to the
organic solvent used insofar as the solvent can dissolve or
disperse the polymer or hydrogenated polymer and does not affect
the polymerization reaction and the hydrogenation reaction. A
common industrially available solvent is preferable.
[0096] As specific examples of such an organic solvent, aliphatic
hydrocarbons such as pentane, hexane, and heptane; alicyclic
hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane,
dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane,
diethylcyclohexane, decahydronaphthalene, bicycloheptane,
tricyclodecane, hexahydroindene cyclohexane, and cyclooctane;
aromatic hydrocarbons such as benzene, toluene, and xylene;
halogen-containing aliphatic hydrocarbons such as dichloromethane,
chloroform, and 1,2-dichloroethane; halogen-containing aromatic
hydrocarbons such as chlorobenzene and dichlorobenzene;
nitrogen-containing hydrocarbons such as nitromethane,
nitrobenzene, and acetonitrile; ethers such as diethyl ether and
tetrahydrofuran; and the like can be given. These organic solvents
may be used either individually or in combinations of two or
more.
[0097] Of these, common industrial solvents such as aromatic
hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and
ethers are preferably used.
[0098] When the polymerization is carried out in an organic
solvent, the concentration of 2-norbornene or the monomer mixture
consisting of 2-norbornene and substituent-containing norbornene
monomers is preferably 1 to 50 wt %, more preferably 2 to 45 wt %,
and particularly preferably 3 to 40 wt %. If the concentration of
2-norbornene or the monomer mixture is less than 1 wt %, the
productivity may be reduced; if more than 50 wt %, the solution
viscosity after polymerization is too high, and there is a
possibility that the subsequent hydrogenation reaction may become
difficult.
[0099] It is preferable to add a molecular weight controlling agent
to the ring-opening polymerization reaction system. The molecular
weight of the ring-open polymer may be adjusted by adding a
molecular weight controlling agent.
[0100] Any molecular weight controlling agent conventionally used
may be used without a particular limitation.
[0101] As examples, .alpha.-olefins such as 1-butene, 1-pentene,
1-hexene, and 1-octene; styrenes such as styrene and vinyltoluene;
ethers such as ethyl vinyl ether, isobutyl vinyl ether, and allyl
glycidyl ether; halogen-containing vinyl compounds such as
allylchloride; oxygen-containing vinyl compounds such as glycidyl
methacrylate; nitrogen-containing vinyl compounds such as
acrylamide; nonconjugated dienes such as 1,4-pentadiene,
1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene,
2-methyl-1,4-pentadiene, and 2,5-dimethyl-1,5-hexadiene; conjugated
dienes such as 1,3-butadiene, 2-methyl-1,3-butadiene,
2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene can
be given. Of these, .alpha.-olefins are preferable due to their
capability of easily adjusting the molecular weight.
[0102] The amount of the molecular weight controlling agent may be
the amount by which the polymers with a desired molecular weight
can be obtained. Such an amount, in terms of molar ratio of the
molecular weight controlling agent to the total amount of all
monomers used, may be usually 1:50 to 1:1,000,000, preferably 1:100
to 1:5,000, and more preferably 1:300 to 1:3,000.
[0103] The polymerization reaction is initiated by mixing
2-norbornene or a monomer mixture of 2-norbornene and
substituent-containing norbornene monomers with a polymerization
catalyst.
[0104] Although not particularly limited, the polymerization
temperature is usually -20.degree. C. to +100.degree. C.,
preferably 10.degree. C. to 80.degree. C., and more preferably
30.degree. C. to 60.degree. C. If the temperature of the
polymerization reaction is too low, the reaction rate may be
reduced. When the polymerization temperature is too high, there is
a possibility that the molecular weight distribution may be
broadened.
[0105] Although not particularly limited, the polymerization
reaction time is usually from one minute to 100 hours.
[0106] The pressure conditions are also not particularly limited.
The polymerization reaction is usually carried out under pressure
of 0 to 1 MPa.
[0107] After the reaction, the target 2-norbornene ring-open
polymer or 2-norbornene ring-open copolymer (hereinafter referred
to from time to time collectively as "norbornene ring-open
polymer") may be isolated by an ordinary post treatment
operation.
[0108] The resulting norbornene ring-open polymer is supplied to
the next hydrogenation reaction step.
[0109] The hydrogenation reaction may also be continuously
performed by adding a hydrogenation catalyst to the ring-opening
polymerization or ring-opening copolymerization reaction solution
without isolating the norbornene ring-open polymer as described
later.
(Hydrogenation Reaction)
[0110] The hydrogenation reaction of the norbornene ring-open
polymer is a reaction of adding hydrogen to the carbon-carbon
double bonds in the main chain of the norbornene ring-open polymer.
The hydrogenation reaction is carried out by adding a hydrogenation
catalyst to a solution of 2-norbornene ring-open (co)polymer in an
inert solvent while supplying hydrogen to the reaction system.
[0111] Any hydrogenation catalyst commonly used for hydrogenating
olefin compounds may be used without specific limitations. The
catalyst may be either a homogeneous catalyst or a heterogeneous
catalyst. A heterogeneous catalyst is preferred when removal of
metals from the resulting polymer or the like is considered.
[0112] As homogeneous catalysts, a catalyst system consisting of a
combination of a transition metal compound and an alkali metal
compound, for example, cobalt acetate and triethylaluminum, nickel
acetylacetonate and triisobutylaluminum, titanocene dichloride and
n-butyllithium, zirconocene dichloride and sec-butyllithium, and
tetrabutoxy titanate and dimethyl magnesium; a noble metal complex
catalyst such as dichloro-bis(triphenylphosphine)palladium,
chlorohydridocarbonyl tris(triphenylphosphine)ruthenium, and
chlorotris(triphenylphosphine)rhodium; and the like can be
given.
[0113] As heterogeneous catalysts, nickel, palladium, platinum,
rhodium, and ruthenium, or solid catalysts with these metals
supported on a carrier such as carbon, silica, diatomaceous earth,
alumina, or titania, for example, nickel on silica, nickel on
diatomaceous earth, nickel on alumina, palladium on carbon,
palladium on silica, palladium on diatomaceous earth, and palladium
on alumina can be given.
[0114] The amount of the catalyst used is usually 0.05 to 10 parts
by weight for 100 parts by weight of the norbornene ring-open
polymer.
[0115] As the inert organic solvent used for the hydrogenation
reaction, the same organic solvents as previously mentioned in
connection with the ring-opening polymerization of 2-norbornene or
the ring-opening copolymerization of 2-norbornene and
substituent-containing norbornene monomers may be given.
[0116] The hydrogenation reaction temperature varies according to
the hydrogenation catalyst used. The reaction temperature is
usually from -20 to +300.degree. C., preferably from 0 to
+250.degree. C., and more preferably from 100 to 200.degree. C. If
the temperature of the hydrogenation reaction is too low, the
reaction rate may be small. When the hydrogenation reaction
temperature is too high, a side reaction may occur.
[0117] After the hydrogenation reaction, the reaction solution is
filtered to remove the hydrogenation catalyst and volatile
components such as a solvent are removed from the polymer solution
after the filtration to obtain the target hydrogenated norbornene
ring-open polymer (I) or (II).
[0118] Since the hydrogenated norbornene ring-open polymers (I) and
(II) of the present invention have good solubility in organic
solvents, the polymer after hydrogenation may be sufficiently
purified by removing residual catalysts and the like.
[0119] As the method of removing the volatile components such as a
solvent from the polymer solution after filtration, known methods
such as a coagulation method, a direct drying method, and the like
can be given.
[0120] A coagulation method is a method of mixing a polymer
solution with a poor solvent for the polymer to precipitate the
polymer. Examples of the poor solvent used include polar solvents
including alcohols such as ethyl alcohol, n-propyl alcohol, and
isopropyl alcohol; ketones such as acetone and methyl ethyl ketone;
and esters such as ethyl acetate and butyl acetate.
[0121] The component in the form of particles obtained by
precipitation is dried by heating under vacuum, in nitrogen, or in
the air to obtain dry particles, or made into pellets by extruding
from a melt extruder.
[0122] A direct dry technique is a method of removing solvents by
heating the polymer solution under reduced pressure. This method
may be carried out using a centrifugal thin-film continuous
vaporization dryer, a surface-scraping heat-exchange continuous
reactor dryer, a high-viscosity reactor, or the like. The degree of
vacuum and the temperature are not particularly limited and are
suitably selected according to the apparatus used.
[0123] The degree of hydrogenation of the main chain double bonds
in the hydrogenated norbornene ring-open polymers (I) and (II)
(hereinafter referred to from time to time as "hydrogenated
ring-open polymer of the present invention") is 80% or more,
preferably 90% or more, more preferably 95% or more, still more
preferably 99% or more, and particularly preferably 99.9% or more.
The degree of hydrogenation of the above range prevents resin
burning when molding and suppresses generation of a die line
particularly when a film is formed.
[0124] The degree of hydrogenation of the hydrogenated ring-open
polymer of the present invention can be determined by .sup.1H-NMR
spectrum measurement using deuteriochloroform as a solvent.
[0125] The hydrogenated norbornene ring-open polymer (I) has a
polystyrene-reduced weight average molecular weight (Mw), measured
by gel permeation chromatography (GPC) using 1,2,4-trichlorobenzene
as an eluant, of 50,000 to 200,000, preferably 70,000 to 180,000,
and more preferably 80,000 to 150,000.
[0126] The hydrogenated norbornene ring-open polymer (II) has a
polystyrene-reduced weight average molecular weight (Mw), measured
by gel permeation chromatography (GPC) using 1,2,4-trichlorobenzene
as an eluant, of preferably 50,000 to 200,000, more preferably
70,000 to 180,000, and particularly preferably 80,000 to
150,000.
[0127] If the Mw is in this range, the hydrogenated ring-open
polymer has good solubility in solvents and can be produced with
excellent productivity, purified with ease, and molded with ease.
The molded article has good mechanical properties and heat
resistance. If the Mw is too large, the polymer solution has high
viscosity and can be filtered only with difficulty, resulting in
impaired productivity. In addition, a high temperature is required
for the resin in order to increase the film thickness precision
when producing a film, resulting in a die line due to burning of
the resin. If the Mw is too small, mechanical properties and heat
resistance of the molded article may decrease.
[0128] In addition, because the hydrogenated ring-open polymer is
crystalline, the hydrogenated polymer dissolves in solvents only
with difficulty, resulting in poor productivity of the polymer and
difficulty in polymer purification.
[0129] If the Mw is in this range, the hydrogenated ring-open
polymer exhibits excellent blister moldability and produces a
molded article with excellent strength. If the Mw is too large,
blister moldability is impaired. It is difficult to mold the resin
by blister molding or, if molded by blister molding, the molded
article may have some defects such as an uneven or deflected
thickness. On the other hand, if the Mw is too small, the blister
molded article may have poor mechanical strength.
[0130] The upper limit of the molecular weight distribution (Mw/Mn)
of the hydrogenated norbornene ring-open polymer (I) of the present
invention is 10.0, preferably 9.0, more preferably 8.5, and still
more preferably 8.0. The lower limit of (Mw/Mn) is 1.5, preferably
2.0, and more preferably 2.5.
[0131] Although not particularly limited, the upper limit of the
molecular weight distribution (Mw/Mn) of the hydrogenated
norbornene ring-open polymer (II) is preferably 10.0, more
preferably 9.0, still more preferably 8.5, and particularly
preferably 8.0. Although there are no particular limitations, the
lower limit of (Mw/Mn) is preferably 1.5, more preferably 2.0, and
still more preferably 2.5.
[0132] If the Mw/Mn is in this range, the hydrogenated ring-open
polymer exhibits excellent blister moldability and produces a
molded article with excellent strength and heat resistance. If the
Mw/Mn is too narrow, the melting viscosity of the hydrogenated
ring-open polymer delicately changes according to a change of
temperature, resulting in impaired processability of the molded
article such as a film and a sheet. In addition, if the resin is
molded by blister molding, the molded article may have some defects
such as an uneven or deflected thickness. On the other hand, if the
Mw/Mn is too broad, the molded article may have poor mechanical
strength and decreased heat resistance.
[0133] The Mn is determined as a standard polystyrene-reduced value
by gel permeation chromatography (GPC) using 1,2,4-trichlorobenzene
as an eluant.
[0134] The hydrogenated ring-open polymer of the present invention
is crystalline and, therefore, has a melting point (hereinafter
referred to from time to time as "Tm"). The melting point of the
hydrogenated ring-open polymer is 110 to 145.degree. C., preferably
120 to 145.degree. C., and more preferably 130 to 145.degree.
C.
[0135] If the Tm is in the above range, the molded article has good
heat resistance. The melting point in a range of 130 to 145.degree.
C. is preferable due to capability of the resin to withstand steam
sterilization when producing molded articles for medical or food
use.
[0136] The melting point of the hydrogenated ring-open polymer is
determined according to JIS K7121 using a general differential
scanning calorimeter.
[0137] The melting point of the hydrogenated ring-open polymer
varies according to the molecular weight, molecular weight
distribution, isomerization degree, copolymerization ratio of
2-norbornene and substituent-containing norbornene monomers, and
the like.
[0138] Since the hydrogenated ring-open polymer of the present
invention has a melting point and, therefore, possesses a
crystalline structure, the polymer forms crystalline areas in the
blister-molded article. The crystalline areas improve the
mechanical properties such as tensile breaking elongation and the
like in combination with amorphous areas. In spite of such
characteristics, the molded article has good transparency because
of the small size crystal.
[0139] The isomerization ratio of the hydrogenated ring-open
polymer of the present invention is usually 0 to 40%, preferably 0
to 20%, more preferably 1 to 10%, and still more preferably 1 to
5%. If the isomerization ratio is too high, the polymer may have
reduced heat resistance. If the isomerization ratio is too low, on
the other hand, the polymer has reduced solubility in solvents,
resulting in poor productivity of the polymer and difficulty in
polymer purification. In addition, the molded article may have
impaired transparency.
[0140] The isomerization ratio of the hydrogenated ring-open
polymer of the present invention can be calculated using an
equation, 33.0 ppm peak integration value/(31.8 ppm peak
integration value+33.0 ppm peak integration value).times.100,
wherein the peak integration values are determined by .sup.13C-NMR
spectrum measurement using deuteriochloroform as a solvent.
[0141] The 31.8 ppm peak is a peak derived from cis-isomers of
2-norbornene repeating units in the hydrogenated ring-open polymer
and the 33.0 ppm peak is a peak derived from trans-isomers of
2-norbornene repeating units in the hydrogenated ring-open
polymer.
[0142] In order to produce a norbornene ring-open polymer having
the isomerization ratio of the above range, the hydrogenation
reaction temperature of the norbornene ring-open polymer is
preferably 100 to 200.degree. C., more preferably 120 to
170.degree. C., and still more preferably 130 to 160.degree. C.,
and the amount of the hydrogenation catalyst should preferably be
0.1 to 5 parts by weight, and more preferably 0.1 to 1 part by
weight for 100 parts by weight of the 2-norbornene ring-open
(co)polymer. Such a hydrogenation reaction temperature and amount
of hydrogenation catalyst are preferable due to the
excellently-balanced hydrogenation degree and heat resistance of
the polymer.
[0143] The hydrogenated ring-open polymer exhibiting the
above-described characteristics is suitable as a resin material
which provides excellent properties such as steam barrier
properties, heat resistance, oil resistance, mechanical properties,
and processability demanded in recent years in the fields of
information processing, food industries, medical supplies,
engineering works, and the like.
2) Resin Composition
[0144] The resin composition of the present invention comprises the
hydrogenated ring-open polymer and an antioxidant.
[0145] The amount of antioxidant to be added is usually 0.01 to 1
part by weight, and preferably 0.05 to 0.5 parts by weight for 100
parts by weight of the hydrogenated ring-open polymer. If the
amount of antioxidant is too small, the molded article may be
easily burnt (colored). On the other hand, if the amount if too
large, the molded article may be whitened or allow the antioxidant
to elute therefrom.
[0146] Although there are no particular limitations, the molecular
weight of the antioxidant used is preferably 700 or more. If the
molecular weight of the antioxidant is too small, the molded
article may allow the antioxidant to elute therefrom.
[0147] As specific examples of the antioxidant, phenolic
antioxidants such as
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methan-
e, and
pentaerythrityltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionat-
e]; phosphorus antioxidants such as triphenylphosphite,
tris(cyclohexylphenyl)phosphite, and
9,10-dihydro-9-oxa-10-phosphaphenanthrene; sulfur-containing
antioxidants such as dimyristyl-3,3'-thiodipropionate,
distearyl-3,3'-thiodipropionate,
laurylstearyl-3,3'-thiodipropionate, and
pentaerythritoltetrakis(.beta.-laurylthiopropionate); and the like
can be given. These antioxidants may be used either individually or
in combination of two or more. Among these, phenolic antioxidants
are preferable.
[0148] In addition to the hydrogenated ring-open polymer and the
antioxidant, the resin composition of the present invention may
include various other additives which are commonly used in
synthetic resins to the extent that the object of the present
invention is not inhibited.
[0149] Examples of the additives include rubber-like polymers and
other resins, UV absorbers, weather-resistant stabilizers,
antistatic agents, slipping agents, anticlouding agents, dyes,
pigments, coloring agents, natural oils, synthetic oils,
plasticizers, organic or inorganic fillers, antibacterial agents,
deodorants, and the like.
[0150] The rubber-like polymers are polymers having a glass
transition temperature of 40.degree. C. or less and include rubbers
and thermoplastic elastomers. When the polymer has two or more
glass transition temperatures such as in the case of a block
copolymer, such a polymer may be used as the rubber-like polymer if
the lowest glass transition temperature is not more than 40.degree.
C. Although the viscosity of the rubber-like polymer may be
suitably selected according to the purpose of use, the Mooney
viscosity (ML.sub.1+4, 100.degree. C.) is usually 5 to 300.
[0151] As examples of the rubber-like polymer, an ethylene
.alpha.-olefin rubber; an ethylene-.alpha.-olefin polyene copolymer
rubber; a copolymer of ethylene and unsaturated carboxylate such as
ethylene methyl methacrylate and ethylene butyl acrylate; a
copolymer of ethylene and a fatty acid vinyl ester such as an
ethylene-vinyl acetate copolymer; a polymer of alkyl acrylate such
as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl
acrylate, and lauryl acrylate; diene rubbers such as polybutadiene,
polyisoprene, a random copolymer of styrene and butadiene or
isoprene, an acrylonitrile-butadiene copolymer, a butadiene
isoprene copolymer, a butadiene-alkyl (meth)acrylate copolymer, a
butadiene-alkyl (meth)acrylate-acrylonitrile copolymer, and a
butadiene-alkyl (meth)acrylate-acrylonitrile-styrene copolymer; a
butylene-isoprene copolymer; block copolymers of aromatic vinyl
conjugated diene such as a styrene-butadiene block copolymer, a
hydrogenated styrene-butadiene block copolymer, a hydrogenated
styrene-butadiene random copolymer, a styrene-isoprene block
copolymer, and a hydrogenated styrene-isoprene block copolymer; a
low crystalline polybutadiene resin, an ethylene-propylene
elastomer, a styrene-grafted ethylene-propylene elastomer, a
thermoplastic polyester elastomer, an ethylene ionomer resin, and
the like can be given.
[0152] The amount of the rubber-like polymers is suitably selected
according to the purpose of use. When impact resistance and
pliability are demanded, the amount of the rubber-like polymers is
usually in a range from 0.01 to 100 parts by weight, preferably
from 0.1 to 70 parts by weight, and more preferably from 1 to 50
parts by weight for 100 parts by weight of the hydrogenated
ring-open polymer.
[0153] As examples of the other resins, an amorphous norbornene
ring-open polymer, an amorphous hydrogenated norbornene ring-open
polymer, an amorphous norbornene addition polymer, a crystalline
norbornene ring-open polymer, a crystalline hydrogenated norbornene
ring-open polymer other than the hydrogenated ring-open polymer of
the present invention, a crystalline norbornene addition polymer, a
low density polyethylene, a high density polyethylene, a linear low
density polyethylene, a super-low density polyethylene, an
ethylene-ethyl acrylate copolymer, an ethylene-vinyl acetate
copolymer, polypropylene, polystyrene, hydrogenated polystyrene,
polymethyl methacrylate, polyvinyl chloride, polyvinylidene
chloride, polyphenylene sulfide, polyphenylene ether, polyamide,
polyester, polycarbonate, cellulose triacetate, polyether imide,
polyimide, polyallylate, polysulfone, polyether sulfone, and the
like can be given.
[0154] These resins may be used either individually or in
combination of two or more in any proportion not affecting the
purpose of the present invention.
[0155] Examples of the UV absorbers and weather-resistant
stabilizers include hindered amine compounds such as
2,2,6,6-tetramethyl-4-piperidyl benzoate,
bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-
-2-n-butyl malonate, and
4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-1-{2-[3-(3,5-di-t-buty-
l-4-hydroxyphenyl)propionyloxy]ethyl}-2,2,6,6-tetramethylpiperidine;
benzotriazole compounds such as
2-(2-hydroxy-5-methylphenyl)benzotriazole,
2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole,
2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, and
2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole; benzoate compounds
such as 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and
hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; and the like.
[0156] These UV absorbers and weather-resistant stabilizers may be
used either individually or in combination of two or more.
[0157] Although there are no specific limitations to the amount of
the UV absorbers and weather-resistant stabilizers, these additives
are usually used in an amount of 0.001 to 5 parts by weight, and
preferably 0.01 to 2 parts by weight for 100 parts by weight of the
hydrogenated ring-open polymer.
[0158] As examples of the antistatic agent, long-chain alkyl
alcohols such as stearyl alcohol and behenyl alcohol; sodium alkyl
sulfonate and/or phosphonium salt of alkyl sulfonic acid; fatty
acid esters such as glycerol ester of stearic acid; hydroxyamine
compounds; amorphous carbon, tin oxide powder, antimony-containing
tin oxide powder; and the like can be given. The antistatic agent
is usually used in an amount of 0.001 to 5 parts by weight for 100
parts by weight of the hydrogenated ring-open polymer.
[0159] As an example of the method for preparing the resin
composition of the present invention, a method of melt-kneading the
hydrogenated ring-open polymer of the present invention together
with the Antioxidant And other optional additives using a
twin-screw kneader, for example, at 200 to 400.degree. C., and
producing pellets, granules, or powder from the kneaded product can
be given.
[0160] The resin composition obtained in this manner has excellent
processability. The film thickness fluctuation, when a monolayer
film is prepared from the hydrogenated ring-open polymer or the
resin composition of the present invention by a known T-die melt
extruder, is usually not more than 10 .mu.m, and preferably not
more than 7 .mu.m. In no case is a die line not produced for a long
time during a continuous film forming operation. The period of time
for which the film can be formed without producing a die line is
usually 10 hours or more, and more preferably 15 hours or more.
[0161] The term "die line" refers to a streak, observable with the
naked eye, continuously generated along the direction of extrusion
of the resin at the position of the molded article corresponding to
the specific position of the die. More specifically, the die line
is a streak formed on the surface of the molded article consisting
of irregularities (concaves and convexes) with a height of about
0.3 .mu.m to 100 .mu.m. Smaller concaves and convexes cannot be
observed with the naked eye.
3) Resin Film or Sheet
[0162] The resin film or sheet of the present invention
(hereinafter referred to from time to time as "resin film and the
like of the present invention") can be obtained by molding the
hydrogenated ring-open polymer or the resin composition of the
present invention.
[0163] There are no specific limitations to the method of molding
the hydrogenated ring-open polymer or the resin composition of the
present invention. Either a heat-melting molding method or a
solution cast method may be used.
[0164] The heat-melting molding method is a method of fluidizing
the molding material by heating at a temperature above Tm, but
lower than the thermal cracking temperature of the polymer, and
molding the fluidized material into a film or sheet. The
heat-melting molding method includes an extrusion molding method, a
calender molding method, a compression molding method, an inflation
molding method, an injection molding method, a blow molding method,
an extension molding method, and the like.
[0165] It is possible to apply the extension molding method to a
film produced by the extrusion molding method, calender molding
method, inflation molding method, or the like.
[0166] The heating conditions and pressure conditions in the
heat-melting molding method may be appropriately selected according
to the type of molding machine and properties of the hydrogenated
ring-open polymer. A temperature in the range usually from Tm to
(Tm+100.degree. C.), and preferably from (Tm+20.degree. C.) to
(Tm+50.degree. C.) is applied under a pressure of usually from 0.5
to 100 MPa, and preferably from 1 to 50 MPa.
[0167] The reaction time is usually from about several seconds to
several tens of minutes.
[0168] The hydrogenated ring-open polymer of the present invention
has a comparatively high Tm and high heat resistance, but becomes
fluid at a temperature between 200.degree. C. and 400.degree. C. by
a remarkable reduction in the viscosity.
[0169] Although the reason is not clear, the polymer is thought to
rapidly decrease in viscosity at a temperature in the above range
by forming a liquid crystal state due to the crystalline
properties. Therefore, the hydrogenated ring-open polymer of the
present invention flows well in spite of the high melting
temperature and can be molded into a film or a sheet in a short
time.
[0170] On the other hand, the solution cast method is a method of
dissolving the resin composition of the present invention in an
organic solvent, casting the solution on a plane or a roll, and
removing the solvent by heating to obtain a film and a sheet.
[0171] As the solvent used, the same solvents as previously
mentioned in connection with the ring-opening polymerization of
2-norbornene, the ring-opening copolymerization of 2-norbornene and
substituent-containing norbornene monomers, and hydrogenation of
the norbornene ring-open polymer may be given.
[0172] The solution cast method is carried out at a temperature at
which the solvent volatilizes. The molding temperature is thus
appropriately determined according to the type of the solvent
used.
[0173] The molded article may be annealed in order to increase
crystallinity.
[0174] There are no specific limitations to the thickness of the
resin film and the like of the present invention. The thickness is
usually 1 .mu.m to 20 mm, preferably 5 .mu.m to 5 mm, and more
preferably 10 .mu.m to 2 mm. A film is not distinguished from a
sheet by any specific definition, although these terms are
sometimes distinguished according to the thickness, the names (film
or sheet) used according to the application and the practice in the
industry.
[0175] Since the hydrogenated ring-open polymer molded into the
film or the like of the present invention has a melting point and,
therefore, possesses a crystalline structure, the polymer forms
crystalline areas in the molded film or sheet. The crystalline
areas improve the mechanical properties such as tensile breaking
elongation and the like in combination with amorphous areas, and
yet allows the film or the sheet to exhibit excellent transparency
due to the small size of the crystals.
[0176] In order to increase the mechanical strength and steam
barrier properties, the film or the sheet may be stretched to
increase the crystallinity. This is an operation of applying
plastic deformation to a sheet or film by stretching the length of
the molded film or sheet 1.1 to 10 times. The plastic deformation
has an effect of orienting amorphous chains, not to mention
crystalline chains, by internal friction caused by stretching.
[0177] The resin film of the present invention may be a laminate of
a layer containing the hydrogenated ring-open polymer and a layer
containing other polymers.
[0178] As the other polymers, rubber-like polymers and other resins
may be given.
[0179] The same polymers and resins previously mentioned as those
used together with the hydrogenated ring-open polymer may be given
as specific examples of such other polymers.
[0180] Although the number of the layers to be laminated is usually
two or three, the film or the sheet may be a multilayer laminate
consisting of more than three layers. The order of the types of
polymers in layers of the three or more multilayer laminate may be
determined according to the purpose and application.
[0181] In addition, it is possible to dispose layers of the same
polymer separated by a layer of another polymer. For example, it is
possible to form a three layer laminate having a layer containing
polystyrene sandwiched between two layers containing the
hydrogenated ring-open polymer, or to form a four layer laminate
having a layer containing a hydrogenated styrene-isoprene block
copolymer disposed on either side of the three layer laminate.
[0182] As the laminating method, a method of pasting two layers by
applying an adhesive between them, a method of bonding a monolayer
or a multilayer film or sheet at a temperature above the melting
point by heat or high frequency, a method of preparing a dispersion
or solution of the hydrogenated ring-open polymer or the other
polymers in an organic solvent, applying the dispersion or solution
to the surface of the film or sheet of the other polymers or the
hydrogenated ring-open polymer, and drying the dispersion of the
solution, and the like can be given.
[0183] A laminate may also be produced by co-extruding the
hydrogenated ring-open polymer and the other polymers from an
extruder.
[0184] The resin film and the like of the present invention have
excellent steam barrier properties, heat resistance, oil
resistance, and mechanical properties such as tensile breaking
elongation. The film and the like have an advantage of a wide
processing temperature range due to the high thermal decomposition
temperature.
[0185] The resin film and the like of the present invention have
excellent mechanical properties. The tensile breaking elongation of
the resin film and the like of the present invention measured based
on ISO 527 is usually 25% or more, and preferably 30% or more.
[0186] The resin film and the like of the present invention have
excellent steam barrier properties. The resin film or sheet of the
present invention with a thickness of 100 .mu.m has a moisture
permeability (g/(m.sup.224 h)) measured based on JIS K7129 (Method
A) of usually 0.5(g/(m.sup.224 h)) or less, and preferably 0.4
(g/(m.sup.224 h)) or less.
[0187] The resin film and the like of the present invention have
excellent oil resistance. In a test comprising preparing a test
specimen with a dimension of 10 mm.times.100 mm.times.1 mm by
heat-pressing the resin composition of the present invention,
applying salad oil to the surface of the test specimen, and
securing the test specimen for one hour to a curved aluminum jig
made by cutting an elliptic cylinder with a height of 10 mm having
an ellipse form side with a major axis of 200 mm and a minor axis
of 80 mm into equal four divisions, the test specimen did not
produce cracks.
[0188] The resin film of the present invention which has these
features can be used for a wide variety of applications in the
fields of food industries, medical supplies, displays, energy,
optical appliances, electric and electronic parts,
telecommunications sector, vehicles, public welfare, civil
engineering and construction, and the like.
[0189] The fields in which the resin film of the present invention
is particularly useful include the fields of food industries,
medical supplies, energy, displays, and the like.
[0190] Applications in the fields of food industries include food
packaging, such as a wrap film, a shrink film, and a film for
blister packages of processed foods such as ham, sausage,
pouch-packed food, and frozen food, dried food, specified health
food, rice, confectionery, and meat, and the like.
[0191] In the medical field, the resin film of the present
invention may be used as a medical bottle plug, an infusion bag, an
intravenous drip bag, a film for a press through package (PTP), a
film for blister packages, and the like.
[0192] In the energy fields, the resin film of the present
invention may be used as an auxiliary component material of a solar
energy power generation system, a fuel-cell peripheral component,
an alcohol-containing fuel system component, and a packing film of
these components.
[0193] In the display field, the resin film of the present
invention may be used as a barrier film, a phase difference film, a
polarization film, an optical diffusion sheet, a condensing sheet,
and the like.
4) Molding Material and Molded Article
[0194] The molding material of the present invention is
characterized by containing a hydrogenated norbornene ring-open
polymer obtained by hydrogenating 80% or more of carbon-carbon
double bonds of a ring-open polymer which is obtained by
ring-opening polymerization of 2-norbornene or a monomer mixture of
2-norbornene and a substituent-containing norbornene monomer, the
proportion of a repeating unit (A) derived from the 2-norbornene
with respect to all repeating units being 90 to 100 wt % and the
proportion of a repeating unit (B) derived from the
substituent-containing norbornene monomer with respect to all
repeating units being 0 to 10 wt %, and the hydrogenated norbornene
ring-open polymer having a melting point of 110 to 145.degree. C.,
the amount of organic substances discharged from the molding
material when heated at 80.degree. C. for 60 minutes being not more
than 1 ppm.
[0195] Specifically, this hydrogenated norbornene ring-open polymer
used as the molding material of the present invention is the same
as the hydrogenated norbornene ring-open polymer of the present
invention described above, except that weight average molecular
weight (Mw) determined by gel permeation chromatography (GPC) or
the molecular weight distribution (Mw/Mn) of the hydrogenated
norbornene ring-open polymer is not particularly limited, when such
a polymer is obtained by hydrogenating 80% or more of main-chain
carbon-carbon double bonds of a ring-open polymer which is obtained
by ring-opening polymerization of 2-norbornene (hydrogenated
2-norbornene ring-open polymer). The polymers mentioned above as
preferable examples of the hydrogenated norbornene ring-open
polymer of the present invention are the preferable hydrogenated
norbornene ring-open polymers used as the molding material of the
present invention.
[0196] The monomer mixture used for producing the hydrogenated
norbornene ring-open polymer used for the molding material of the
present invention comprises usually 90 to 100 wt %, preferably 95
to 99 wt %, and more preferably 97 to 99 wt % of 2-norbornene and
usually 0 to 10 wt %, preferably 1 to 5 wt %, and more preferably 1
to 3 wt % of substituent-containing norbornene monomers.
[0197] The proportion of the repeating unit (A) derived from
2-norbornene with respect to all repeating units of the
hydrogenated norbornene ring-open polymer used for the molding
material of the present invention is usually 90 to 100 wt %,
preferably 95 to 99 wt %, and more preferably 97 to 99 wt %, and
the proportion of the repeating unit (B) derived from the
substituent-containing norbornene monomer with respect to all
repeating units of the hydrogenated norbornene ring-open polymer is
0 to 10 wt %, preferably 1 to 5 wt %, and more preferably 1 to 3 wt
%.
[0198] If the proportion of the repeating units (B) is within the
above range, the resin has excellent heat resistance and discharges
only a very small amount of organic substances, and the resulting
molded article generates resin powder (foreign matter) by friction
and the like only with difficulty. If the proportion of the
repeating units (B) is too large, the resin may have impaired heat
resistance and may discharge an increased amount of organic
substances, and the resulting molded article tends to generate
foreign matter by friction and the like with ease. If the
proportion of the repeating units (B) is too small, the resulting
molded article tends to easily generate foreign matter by
friction.
[0199] The molding material of the present invention comprises one
or more of the above hydrogenated norbornene ring-open polymers
and, to an extent not affecting the object of the present
invention, may optionally contain additives such as an antioxidant
(stabilizer), an UV absorber, a weather-resistant stabilizer, an
antistatic agent, other polymers such as a thermoplastic resin and
a soft polymer, a lubricant, and the like.
[0200] The content of the hydrogenated norbornene ring-open polymer
in the molding material of the present invention is usually 50 wt %
or more, preferably 70 wt % or more, and more preferably 90 wt % or
more. When the content is in this range, heat resistance and other
characteristics such as the properties of discharging a minimal
amount of organic compounds are not affected.
[0201] If an antioxidant is added, a molded article of which the
mechanical strength is reduced only with difficulty can be
obtained.
[0202] There are no specific limitations to the antioxidant. A
phenol-based antioxidant, a phosphorus-containing antioxidant, a
sulfur-containing antioxidant, a sulfur-containing antioxidant, a
lactone-containing antioxidant, and the like can be given as
examples.
[0203] As the phenol-based antioxidant, known phenol-based
antioxidants such as acrylate phenol compounds disclosed in
JP-A-63-179953 and JP-A-1-168643 such as
2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate and
2,4-di-t-amyl-6-(1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl)phenylacrylat-
e;
alkyl-substituted phenol compounds such as
2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol,
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
2,2'-methylene-bis(4-methyl-6-t-butylphenol),
4,4'-butylidene-bis(6-t-butyl-m-cresol),
4,4'-thio-bis(3-methyl-6-t-butylphenol),
bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane,
3,9-bis(2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimeth-
ylethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane,
1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,
tetrakis(methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenylpropionate)methane-
) [e.g.
pentaerythrimethyltetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propi-
onate)], triethylene glycol
bis(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate), and
tocophenol; triazine group-containing phenol compounds such as
6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bisoctylthio-1,3,5-triazine,
6-(4-hydroxy-3,5-dimethylanilino)-2,4-bisoctylthio-1,3,5-triazine,
6-(4-hydroxy-3-methyl-5-t-butylanilino)-2,4-bisoctylthio-1,3,5-triazine,
and
2-octylthio-4,6-bis-(3,5-di-t-butyl-4-oxyanilino)-1,3,5-triazine;
and the like can be given.
[0204] As the phosphorous-containing antioxidant, known
phosphorous-containing antioxidants including mono-phosphite
compounds such as triphenyl phosphite, diphenylisodecyl phosphite,
phenyldiisodecyl phosphite, tris(nonylphenyl)phosphite,
tris(dinonylphenyl) phosphite, tris(2,4-di-t-butylphenyl)phosphite,
tris(2-t-butyl-4-methylphenyl)phosphite,
tris(cyclohexylphenyl)phosphite,
2,2-methylene-bis(4,6-di-t-butylphenyl)octylphosphite,
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanth-
rene-10-oxide, and
10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene;
diphosphite compounds such as
4,4'-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecylphosphite),
4,4'-isopropylidene-bis(phenyl-di-alkyl(C.sub.12 to
C.sub.15)phosphite),
4,4'-isopropylidene-bis(diphenyl-mono-alkyl(C.sub.12 to C.sub.15)
phosphite),
1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane,
tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylenediphosphite, cyclic
neopentan-tetra-yl-bis(iso-decylphosphite),
cyclicneopentan-tetra-yl-bis(nonylphenylphosphite),
cyclicneopentan-tetra-yl-bis(2,4-di-t-butylphenylphosphite),
cyclicneopentan-tetra-yl-bis(2,4-dimethylphenylphosphite), cyclic
neopentan-tetra-yl-bis(2,6-di-t-butylphenylphosphite); and the like
can be given.
[0205] Examples of sulfur-containing antioxidants include dilauryl
3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl
3,3-thiodipropionate, laurylstearyl 3,3-thiodipropionate,
pentaerythritoltetrakis(.beta.-laurylthiopropionate),
3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane,
and the like.
[0206] Although any compounds containing a lactone structure may be
used as a lactone-based antioxidant without particular limitation,
an aromatic lactone compound is preferable, and a compound having a
benzofuranone skeleton is more preferable, with
3-arylbenzofuran-2-one having an aryl group as a substituent on the
side chain of the furan ring being even more preferable. As an
specific example,
5,7-di-t-butyl-3-(3,4-di-methylphenyl)-3H-benzofuran-2-one can be
given.
[0207] Among these antioxidants, an alkyl-substituted phenolic
antioxidant is particularly preferable in the present invention. In
order to prevent volatilization, an antioxidant with a vapor
pressure of not higher than 10.sup.-6 Pa at 20.degree. C. is
preferable.
[0208] The antioxidants may be used either individually or in
combination of two or more.
[0209] The amount of the antioxidant used in the present invention
may be appropriately determined in a range not impairing the effect
of the present invention. Such an amount is usually from 0.001 to 5
parts by weight, and preferably from 0.01 to 1 part by weight for
100 parts by weight of the hydrogenated ring-open polymer.
[0210] Examples of the UV absorbers and weather-resistant
stabilizers include hindered amine compounds such as
2,2,6,6-tetramethyl-4-piperidyl benzoate,
bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-
-2-n-butyl malonate, and
4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-1-{2-[3-(3,5-di-t-buty-
l-4-hydroxyphenyl)propionyloxy]ethyl}-2,2,6,6-tetramethylpiperidine;
benzotriazole compounds such as 2-(2-hydroxy-5-methyl
phenyl)benzotriazole,
2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole,
2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, and
2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole; benzoate compounds
such as 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and
hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; and the like. These UV
absorbers and weather-resistant stabilizers may be used either
individually or in combination of two or more.
[0211] The amount of the UV absorbers and weather-resistant
stabilizers is usually from 0.001 to 5 parts by weight, and
preferably 0.01 to 2 parts by weight for 100 parts by weight of the
hydrogenated ring-open polymer.
[0212] The antistatic agent is added to provide an antistatic
effect.
[0213] As examples of the antistatic agent, long-chain alkyl
alcohols such as stearyl alcohol and behenyl alcohol; sodium alkyl
sulfonate and/or phosphonium salt of alkyl sulfonic acid; fatty
acid esters such as glycerol ester of stearic acid; hydroxyamine
compounds; amorphous carbon, tin oxide powder, antimony-containing
tin oxide powder; and the like can be given.
[0214] The antistatic agent is usually used in an amount of 0.001
to 50 parts by weight for 100 parts by weight of the hydrogenated
ring-open polymer.
[0215] Other polymers such as a thermoplastic resin and a soft
polymer are added in order to improve mechanical properties and
moldability.
[0216] As examples of the thermoplastic resin, polyolefins such as
low density polyethylene, high density polyethylene, linear low
density polyethylene, super-low density polyethylene,
polypropylene, polybutene, and polypentene; polyesters such as
polyethyleneterephthalate and polybuthyleneterephthalate;
polyamides such as nylon 6 and nylon 6,6; ethylene-ethyl acrylate
copolymer, ethylene-vinyl acetate copolymer, polystyrene,
polyphenylene sulfide, polyphenylene ether, polyamide, polyester,
polycarbonate, and the like can be given.
[0217] As the soft polymer, a polymer of which at least one glass
transition temperature (Tg) is 40.degree. C. or less may be used
without particular limitation. For example, random or block
copolymers of an aromatic vinyl monomer and a conjugated diene type
monomer and hydrogenated product thereof such as a
styrene-butadiene block copolymer, a styrene-butadiene-styrene
block copolymer, a styrene-isoprene block copolymer, a
styrene-isoprene-styrene block copolymer, and a styrene-butadiene
random copolymer; polyisopropyrene rubber; polyolefin rubbers such
as an ethylene-propylene copolymer, an ethylene-.alpha.-olefin
copolymer, and a propylene-.alpha.-olefin copolymer; diene
copolymers such as an ethylene-propylene-diene copolymer, an
.alpha.-olefin-diene copolymer, a diene copolymer, an
isobutylene-isoprene copolymer, and an isobutylene-diene copolymer;
norbornene-based rubbers such as a copolymer of a norbornene
monomer and ethylene, or an .alpha.-olefin, a ternary copolymer of
a norbornene monomer and ethylene or an .alpha.-olefin, and a
ring-open polymer of a norbornene monomer; and the like can be
given.
[0218] A lubricant is added in order to improve moldability.
[0219] As a lubricant, a partial ester of a polyhydric alcohol, a
full ester of a polyhydric alcohol (a compound in which 95% or more
of alcoholic hydroxyl groups of polyhydric alcohol is esterified),
a saturated higher alcohol, a partial ether of a polyhydric
alcohol, and the like can be given. Of these, the full ester of
polyhydric alcohol is preferable, with a full ester of a polyhydric
alcohol and an OH group-containing saturated higher fatty acid and
a saturated higher fatty acid being particularly preferable. In
order to prevent volatilization during molding, a lubricant with a
vapor pressure of not higher than 10.sup.-6 Pa at 20.degree. C. is
preferable.
[0220] Although the amount of lubricant may be appropriately
selected according to the purpose of use, the lubricant is usually
used in an amount of 0.001 to 10 parts by weight, and preferably
0.01 to 5 parts by weight for 100 parts by weight of the
hydrogenated ring-open polymer.
[0221] The molding material of the present invention may further
contain other additives such as a light stabilizer, a near-infrared
absorbent, a coloring agent such as a dye and a pigment, a
lubricant, a plasticizer, an anti blocking agent, a fluorescent
bleach, a deodorant, an organic or inorganic filler, a crosslinking
agent, a vulcanizing agent, a wax, and the like.
[0222] The amount of these other additives may be arbitrarily
determined to the extent that the object of the present invention
is not impaired.
[0223] When the molding material of the present invention is a
resin composition, there are no specific limitations to the method
for preparing the resin composition. A method of melting and mixing
the hydrogenated ring-open polymer and the additives using a
kneader such as a mono-axial extruder, biaxial extruder, a roller,
a Banbury mixer, and the like may be given.
[0224] The amount of organic substances discharged from the molding
material of the present invention when heated at 80.degree. C. for
60 minutes is not more than 1 ppm, preferably not more than 150
ppb, more preferably not more than 50 ppb, more preferably not more
than 20 ppb, and particularly preferably not more than 10 ppb. If
the amount of organic substances discharged from the molding
material is in the above range, there will be no possibility that
the resulting molded articles discharge organic substances. A
molding material providing this property is preferable particularly
when the molded article is a wafer carrier for semiconductor
production, since the wafer is not polluted with the organic
substances.
[0225] The amount of organic substances discharged may be
determined by, for example, a method of washing 5 g of the molding
material sample with a large amount of ultra pure water in a clean
room (class 1000), placing the sample in a glass sample container
completely free from moisture and organic substances adhering to
the surface, heating the sample container at 80.degree. C. for 60
minutes, and measuring gases discharged from the sample container
by a heat desorption gas chromatography mass spectrometer (e.g.
TDS-GC-MS manufactured by Agilent Technologies).
[0226] In order to obtain the molding material discharging not more
than 1 ppm of organic substances when heated at 80.degree. C. for
60 minutes, it is only necessary to remove as many volatile
components such as solvents as possible from the hydrogenated
ring-open polymer after filtration.
[0227] As the method of removing the solvents and the like, a
coagulation method, a direct drying method, and the like can be
given.
[0228] The coagulation method is a method of removing solvents by
mixing the polymer solution with a poor solvent for the polymer to
precipitate the polymer and separating the coagulated components
from the liquid.
[0229] Examples of the poor solvent used include polar solvents
such as alcohols such as, for example, methyl alcohol, ethyl
alcohol, n-propyl alcohol, and isopropyl alcohol; ketones such as
acetone and methyl ethyl ketone; and esters such as ethyl acetate
and butyl acetate.
[0230] After separating the coagulated components from the liquid,
it is preferable that the resulting small polymer crumb be heated
and dried to remove the solvent.
[0231] A direct drying technique is a method of removing solvents
by heating the polymer solution under reduced pressure. This method
may be carried out using a commonly known apparatus, for example, a
thin film drier such as a centrifugal thin-film continuous
vaporization dryer, a surface-scraping heat-exchange continuous
reactor dryer, a high-viscosity reactor, or the like. The degree of
vacuum and the temperature are not particularly limited and are
suitably selected according to the apparatus used.
[0232] After removing the solvent by the coagulation method or the
direct drying technique, it is preferable to further heat and dry
under reduced pressure of usually 10 kPa or less, and preferably 3
kPa or less at a temperature of usually 200.degree. C. or more,
preferably 220.degree. C. or more, and more preferably 240.degree.
C. or more. These drying conditions allow almost no unreacted
monomers and solvents to remain in the polymer and thus reduce
organic substances volatilizing from the formed articles.
[0233] It is preferable that the content of transition metals of
the molding material of the present invention be not more than 1
ppm. If the content of transition metals is not more than 1 ppm,
there is no possibility of elusion of metals from the molded
articles. When the molded article is a wafer carrier for
semiconductor production, this feature of the present invention is
particularly preferable. Since metals are not eluted by washing
with an acid or alkali, the wafer carrier is not polluted with the
eluted metals.
[0234] There are no particular limitations to the type of
transition metals. These metals are mixed in from the
polymerization catalyst, hydrogenation catalyst, environmental
foreign matter, and manufacturing equipment, and mainly originate
from the polymerization catalyst and hydrogenation catalyst used in
the process.
[0235] The content of transition metals in the molding material may
be determined by inductively coupled plasma optical emission
spectrometry using, for example, IRIS Advantage/SSEA, manufactured
by Nippon Jarrell-Ash Co. Ltd.
[0236] As a method for obtaining the molding material with a
transition metal content of not more than 1 ppm, a method of
hydrogenating the ring-open polymer using a heterogeneous catalyst
and filtering the resulting hydrogenation reaction solution, a
method of treating the solution of the hydrogenated ring-opening
polymer or the solution of the resin composition obtained by adding
the additives to the hydrogenated ring-opening polymer (hereinafter
referred to from time to time as "resin solution") with an
adsorbent to adsorb the metal atoms, a method of repeatedly washing
the resin solution with an acidic solution and pure water in turn,
and the like can be given. Among these methods, the method of
hydrogenation using a heterogeneous catalyst and filtering the
resulting hydrogenation reaction solution is preferable.
[0237] As the method for hydrogenation using a heterogeneous
catalyst and filtering the resulting hydrogenation reaction
solution, a method of hydrogenating using a heterogeneous catalyst,
followed by (i) filtering the hydrogenation reaction solution
through a filter having a charge capturing function or (ii)
filtering the hydrogenation reaction solution at least twice using
a mechanical filter having pores with a diameter of 0.5 .mu.m or
less, preferably 0.3 .mu.m or less, may be given.
[0238] Among these, the method (i) is preferred because the method
(i) has high capability of removing fine foreign matter which may
pass through pores of a mechanical filter and preventing
regeneration of foreign matter due to re-coagulation after
filtration.
[0239] The filter having a charge capturing function is a filter
which can capture and remove electrically-charged foreign matter.
As the filter having a charge capturing function, a filter of which
the filtering material is charged, for example, a zeta potential
filter which is controlled by a zeta potential, can be given.
[0240] As the zeta potential filter, a filter made from a material
provided with a cationic charge modifier and the like may be
given.
[0241] As examples of the cationic charge modifier, a cellulose
fiber/silica/cationic charge modifier (polyamine epichlorohydrin
resin, aliphatic polyamine, etc.) described in Published Japanese
Translation of PCT Application 4-504379, etc., melamine
formaldehyde cationic colloid, inorganic cationic colloidal silica,
and the like may be given.
[0242] In addition, a product commercially available from CUNO K.K.
under the trademark of "Zeta Plus" may be used as a filter made
from a material provided with a cationic charge modifier.
[0243] Furthermore, in order to increase the processing capacity, a
mechanical filter may be used in combination with the filter having
a charge capturing function. From the viewpoint of processing
efficiency, it is preferable that the hydrogenation reaction
solution be first filtered by a mechanical filtration, and then by
the charge capture function.
[0244] Any mechanical filters which are not damaged by a solvent
may be used without particular limitation. For example, fiber
filters or membrane filters made from polypropylene, polyethylene,
or PTFE; fiber filters made from cellulose; glass fiber filters;
filters made from an inorganic substance such as diatomaceous
earth; and filters made from a metal fiber can be given.
[0245] Although not particularly limited, the pore diameter of the
mechanical filters is usually 10 .mu.m or less, preferably 5 .mu.m
or less, and more preferably 1 .mu.m or less. Either one mechanical
filter or a combination of two or more mechanical filters may be
used.
[0246] The molding material of the present invention also exhibits
excellent heat resistance. The heat resistance of the molding
material of the present invention may be confirmed by, for example,
allowing a wafer carrier for semiconductor production produced from
the molding material to stand at a temperature of 105.degree. C.
for 30 minutes and observing whether or not the wafer carrier is
deformed. No deformation will be found in the wafer carrier
produced from the molding material of the present invention.
[0247] For ease of handling during a molding operation, the molding
material of the present invention is processed into grains the size
of rice called pellets.
[0248] The molded article according to the present invention is
obtained by forming the molding material of the present
invention.
[0249] There are no specific limitations to the shape and size of
the molded article of the present invention. The molded article of
the present invention includes a product of which a part is molded
from the molding material of the present invention.
[0250] The molded article of the present invention can be produced
by a known molding method using the molding material of the present
invention. As the molding method, injection molding, calender
molding, inflation molding, extrusion blow molding, injection blow
molding, multilayer blow molding, connection blow molding, double
wall blow molding, stretch blow molding, vacuum molding, rotational
molding, press molding, melt extrusion molding, and the like can be
given. Among these methods, injection molding is preferable from
the viewpoint of mass production.
[0251] A known injection molding machine may be used for injection
molding.
[0252] The resin temperature (cylinder temperature) is usually from
(Tm+5.degree. C.) to (Tm+200.degree. C.), and preferably from
(Tm+20.degree. C.) to (Tm+150.degree. C.).
[0253] The cylinder residence time of the molding material of the
present invention is usually within one hour, preferably within 30
minutes, and more preferably within 10 minutes. When the molding
material is injection-molded under these conditions, the thermal
decomposition (degradation) of the resin is prevented and
generation of low molecular weight organic compounds is
controlled.
[0254] When a certain period of time is required before molding the
molding material after preparation, the prepared molding material
is preferably stored in a sealed container, for example, a
stainless container.
[0255] The molded article obtained in this manner produces foreign
matter such as resin powder by friction or the like only with
difficulty.
[0256] The difficulty in producing foreign matter from the molded
article can be confirmed as follows, for example. First, in a clean
room (class 1000), an 8-inch new bear silicon wafer purchased in a
state packed in a polypropylene wafer shipper is immersed in a 4.5
wt % solution of hydrofluoric acid at 25.degree. C. for one minute
to remove a thin silicon oxide film. Next, the silicon wafer is
immersed in a 50:1 (volume ratio) mixed solution of 98%
concentrated sulfuric acid and 30% aqueous solution of hydrogen
peroxide at 110.degree. C. for 10 minutes, then in concentrated
sulfuric acid at 65.degree. C. for 10 minutes to remove organic
substances. Next, after washing away acids with a large amount of
ultra-pure water and completely removing the water by a centrifugal
separator, the number of foreign matter particles on the dried
wafer is counted using a foreign matter detector (for example,
Surfscan SP1 manufactured by KLA-Tencor corp.). After the wafer is
inserted in and removed from the molded wafer carrier 50 times, the
number of foreign matter particles on the wafer is counted again.
The increase in the number of foreign matter particles in the test
is usually 250 or less, preferably 230 or less, and more preferably
200 or less.
[0257] Since the molded article of the present invention has
excellent heat resistance, discharges only a small amount of
organic substances, and generates only a small amount of foreign
matter, the molded article can be suitably used as a material for
fabricating electron processing instruments. More particularly,
such electron processing instruments include (A) instruments coming
in contact with electronic parts such as semiconductors such ICs
and LSIs, hybrid ICs liquid crystal display elements, and light
emitting diodes, (B) instruments coming in contact with
intermediate materials such as a wafer, a liquid crystal substrate,
and a product obtained by laminating a transparent electrode layer,
a protective layer, etc. with the wafer or liquid crystal
substrate, and (C) instruments coming in contact with a process
solution used for treating an intermediate material in the
manufacturing process of electronic parts such as a chemical
solution or ultra-pure water.
[0258] As (A) an instrument coming in contact with electronic parts
and (B) an instrument coming in contact with an intermediate
material for manufacturing electronic parts, containers for
processing or transporting such as a tank, a tray, a carrier, a
case, or a shipper; protective materials such as a carrier tape and
a separation film; and the like can be given. As the instruments
(C) coming in contact with a process solution, piping instruments
such as a pipe, a tube, a valve, a flowmeter, a filter, and a pump;
fluid containers such as a sampling container, a bottle, an
ampoule, and a bag; and the like can be given.
[0259] Among these, the wafer carrier for semiconductor production
is particularly preferable. Since the surface of the wafer carrier
for semiconductor production of the present invention is damaged or
has foreign matter attached thereto only with difficulty during
storage and transportation, electronic parts and the like with high
accuracy can be obtained by using the wafer carrier for
semiconductor production of the present invention.
[0260] The molded article of the present invention may also be used
as optical recording media such as an optical disc (e.g. a CD, a
CD-ROM, a laser disc, a digital videodisc, etc.), an optical card,
and an optical tape; an optical lens, a prism, a beam splitter, a
lens prism, an optical mirror, an optical fiber, an LED sealing
material, a substrate for liquid crystal display, a film for liquid
crystal display, a lightguide plate for liquid crystal display, an
optical film, a packing container for food, a packing container
medical supplies, and the like.
[0261] The wafer carrier for semiconductor production of the
present invention (hereinafter may be referred to from time to time
as "carrier") must have a structure enabling the wafers to be held,
removed, and inserted without causing them to come in contact with
each other, and to be subjected to heat treatment or chemical
treatment by dipping or the like. Specifically, the wafers must be
stored with planes held in parallel without coming into contact
with each other and each wafer must be removed or inserted in the
direction parallel to the plane.
[0262] Specifically, the wafers can be stored in a state in which a
wafer and a space are alternately arranged up in layers so that the
wafers are held in a framework provided with grooves or projections
immovable in any direction except for the extraction direction. In
addition, in order to ensure efficient and uniform heat treatment
and dipping in chemicals, the wafer carrier has an inlet port for
allowing a liquid or the like to flow into the spaces between the
wafers from a direction other than the wafer extracting
direction.
[0263] Specific examples of such carriers include those described
in JP-A-2-63112, JP-A-2-143545, JP-A-2-161745, JP-A-3-95954, the
carrier described in FIG. 1, and those specified in the SEMI
specification.
5) Multilayer Laminate
[0264] The multilayer laminate of the present invention is a
laminate having two or more resin layers. At least one layer is a
layer of a hydrogenated norbornene ring-open polymer obtained by
hydrogenating 80% or more of carbon-carbon double bonds of a
ring-open polymer which is obtained by ring-opening polymerization
of 2-norbornene or a monomer mixture of 2-norbornene and a
substituent-containing norbornene monomer. The proportion of the
repeating unit (A) derived from the 2-norbornene with respect to
all repeating units is 90 to 100 wt % and the proportion of the
repeating unit (B) derived from the substituent-containing
norbornene monomer with respect to all repeating units is 0 to 10
wt %, and the hydrogenated norbornene ring-open polymer has a
melting point of 110 to 145.degree. C.
[0265] Specifically, the hydrogenated norbornene ring-open polymer
used as the multilayer laminate of the present invention is the
same as the hydrogenated norbornene ring-open polymer of the
present invention described above, except that weight average
molecular weight (Mw) determined by gel permeation chromatography
(GPC) or the molecular weight distribution (Mw/Mn) of hydrogenated
norbornene ring-open polymer is not particularly limited if such a
polymer is obtained by hydrogenating 80% or more of main-chain
carbon-carbon double bonds of a ring-open polymer which is obtained
by ring-opening polymerization of 2-norbornene (hydrogenated
2-norbornene ring-open polymer). The polymers mentioned above as
preferable examples of the hydrogenated norbornene ring-open
polymer of the present invention are the preferable hydrogenated
norbornene ring-open polymers used as the multilayer laminate of
the present invention.
[0266] The monomer mixture used for producing the hydrogenated
norbornene ring-open polymer used for the multilayer laminate of
the present invention comprises usually 90 to 100 wt %, preferably
95 to 99 wt %, and more preferably 97 to 99 wt % of 2-norbornene
and usually 0 to 10 wt %, preferably 1 to 5 wt %, and more
preferably 1 to 3 wt % of substituent-containing norbornene
monomers.
[0267] The proportion of the repeating unit (A) derived from
2-norbornene with respect to all repeating units of the
hydrogenated norbornene ring-open polymer used for the multilayer
laminate of the present invention is usually 90 to 100 wt %,
preferably 95 to 99 wt %, and more preferably 97 to 99 wt %, and
the proportion of the repeating unit (B) derived from the
substituent-containing norbornene monomer with respect to all
repeating units of the hydrogenated norbornene ring-open polymer is
0 to 10 wt %, preferably 1 to 5 wt %, and more preferably 1 to 3 wt
%.
[0268] Various additives may be added to the hydrogenated
norbornene ring-open polymer used for the multilayer laminate of
the present invention according to the purpose of application.
Examples of the additives include antioxidants, rubber-like
polymers and other resins, UV absorbers, weather-resistant
stabilizers, antistatic agents, slipping agents, anticlouding
agents, dyes, pigments, coloring agents, natural oils, synthetic
oils, plasticizers, organic or inorganic fillers, antibacterial
agents, deodorants, and the like.
[0269] An antioxidant having a molecular weight of 700 or more is
preferably used. If the molecular weight of the antioxidant is too
small, the molded article may allow the antioxidant to elute
therefrom.
[0270] As specific examples of the antioxidant, phenolic
antioxidants such as
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methan-
e, and pentaerythrityl
tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]; phosphorus
antioxidants such as triphenylphosphite,
tris(cyclohexylphenyl)phosphite, and
9,10-dihydro-9-oxa-10-phosphaphenanthrene; sulfur-containing
antioxidants such as dimyristyl-3,3'-thiodipropionate,
distearyl-3,3'-thiodipropionate,
laurylstearyl-3,3'-thiodipropionate, and
pentaerythritoltetrakis(.beta.-laurylthiopropionate); and the like
can be given. These antioxidants may be used either individually or
in combination of two or more. Among these, phenolic antioxidants
are preferable.
[0271] The amount of the antioxidant to be added is usually 0.01 to
1 part by weight, and preferably 0.05 to 0.5 parts by weight for
100 parts by weight of the hydrogenated norbornene ring-open
polymer. If the amount of the antioxidant is too small, the molded
article may be burnt (colored) with ease. On the other hand, if the
amount is too large, the molded article may be whitened or allow
the antioxidant to elute therefrom.
[0272] The rubber-like polymers are polymers having a glass
transition temperature of 40.degree. C. or less and include rubbers
and thermoplastic elastomers. When the polymer has two or more
glass transition temperatures as in the case of a block copolymer,
such a polymer may be used as the rubber-like polymer if the lowest
glass transition temperature is not more than 40.degree. C.
Although the viscosity of the rubber-like polymer may be suitably
selected according to the purpose of use, the Mooney viscosity
(ML.sub.1+4, 100.degree. C.) is usually 5 to 300.
[0273] As examples of the rubber-like polymer, an
ethylene-.alpha.-olefin rubber; an ethylene-.alpha.-olefin polyene
copolymer rubber; a copolymer of ethylene and unsaturated
carboxylate such as ethylene-methyl methacrylate and ethylene-butyl
acrylate; a copolymer of ethylene and a fatty acid vinyl ester such
as an ethylene-vinyl acetate copolymer; a polymer of alkyl acrylate
such as ethyl acrylate, butyl acrylate, hexyl acrylate,
2-ethylhexyl acrylate, and lauryl acrylate; diene rubbers such as
polybutadiene, polyisoprene, a random copolymer of styrene and
butadiene or isoprene, an acrylonitrile butadiene copolymer, a
butadiene isoprene copolymer, a butadiene-alkyl (meth)acrylate
copolymer, a butadiene-alkyl (meth)acrylate-acrylonitrile
copolymer, and a butadiene-alkyl (meth)acry
late-acrylonitrile-styrene copolymer; a butylene-isoprene
copolymer; block copolymers of aromatic vinyl conjugated diene such
as a styrene-butadiene block copolymer, a hydrogenated
styrene-butadiene block copolymer, a hydrogenated styrene-butadiene
random copolymer, a styrene-isoprene block copolymer, and a
hydrogenated styrene-isoprene block copolymer; a low crystalline
polybutadiene resin, an ethylene-propylene elastomer, a
styrene-grafted ethylene-propylene elastomer, a thermoplastic
polyester elastomer, an ethylene ionomer resin, and the like can be
given.
[0274] The amount of the rubber-like polymers is suitably selected
according to the purpose of use. When impact resistance and
pliability are demanded, the amount of the rubber-like polymers is
usually in a range from 0.01 to 100 parts by weight, preferably
from 0.1 to 70 parts by weight, and more preferably from 1 to 50
parts by weight for 100 parts by weight of the hydrogenated
norbornene ring-open polymer.
[0275] As examples of the other resins, an amorphous norbornene
ring-open polymer, an amorphous hydrogenated norbornene ring-open
polymer, a crystalline norbornene addition polymer, an amorphous
norbornene addition polymer, a low density polyethylene, a high
density polyethylene, a linear low density polyethylene, a
super-low density polyethylene, an ethylene-ethyl acrylate
copolymer, an ethylene-vinyl acetate copolymer, polypropylene,
polystyrene, hydrogenation polystyrene, polymethyl methacrylate,
polyvinyl chloride, polyvinylidene chloride, polyphenylene sulfide,
polyphenylene ether, polyamide, polyester, polycarbonate, cellulose
triacetate, polyether imide, polyimide, polyallylate, polysulfone,
polyether sulfone, and the like can be given. These resins may be
used either individually or in combination of two or more in any
proportion not affecting the purpose of the present invention.
[0276] Examples of the UV absorbers and the weather-resistant
stabilizers include hindered amine compounds such as
2,2,6,6-tetramethyl-4-piperidyl benzoate,
bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-
-2-n-butyl malonate, and
4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-1-{2-[3-(3,5-di-t-buty-
l-4-hydroxyphenyl)propionyloxy]ethyl}-2,2,6,6-tetramethylpiperidine;
benzotriazole compounds such as
2-(2-hydroxy-5-methylphenyl)benzotriazole,
2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole,
2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, and
2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole; benzoate compounds
such as 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and
hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; and the like. These UV
absorbers and the weather-resistant stabilizers may be used either
individually or in combination of two or more. The amount of the UV
absorbers and the weather-resistant stabilizers is usually from
0.001 to 5 parts by weight, and preferably 0.01 to 2 parts by
weight for 100 parts by weight of the hydrogenated norbornene
ring-open polymer.
[0277] As examples of the antistatic agent, long-chain alkyl
alcohols such as stearyl alcohol and behenyl alcohol; sodium
alkylsulfonate and/or phosphonium salt of alkylsulfonic acid; fatty
acid esters such as glycerol ester of stearic acid; hydroxyamine
compounds; amorphous carbon, tin oxide powder, antimony-containing
tin oxide powder; and the like can be given. The antistatic agent
is usually used in an amount of 0.001 to 5 parts by weight for 100
parts by weight of the hydrogenated norbornene ring-open
polymer.
[0278] There are no particular limitations to the multilayer
laminate of the present invention insofar as the multilayer
laminate has two or more resin layers of which at least one layer
is a layer containing the hydrogenated ring-open polymer of the
present invention. There are also no particular limitations to the
other layers (hereinafter may be referred to from time to time as a
"synthetic resin layer").
[0279] The content of the hydrogenated norbornene ring-open polymer
in the layer which contains the hydrogenated norbornene ring-open
polymer in the multilayer laminate of the present invention is
usually 50 to 100 wt %, preferably 70 to 100 wt %, and more
preferably 90 to 100 wt %. When the content is in this range, the
characteristics possessed by the hydrogenated norbornene ring-open
polymer such as steam barrier properties are not affected.
[0280] Although there are no specific limitations, the thickness of
the layer containing the hydrogenated norbornene ring-open polymer
is usually 1 to 900 .mu.m, preferably 10 to 400 .mu.m, and more
preferably 20 to 200 .mu.m. This thickness range is preferable
because the characteristics possessed by the hydrogenated
norbornene ring-open polymer such as steam barrier properties are
not affected.
[0281] When the multilayer laminate of the present invention is
used for medical application or as a food packing material, it is
preferable that at least one of the synthetic resin layers is a
layer containing a gas barrier resin.
[0282] A multilayer laminate with excellent steam barrier
properties, as well as excellent gas barrier properties, can be
obtained by using the layer containing a gas barrier resin as the
synthetic resin layer.
[0283] Since oxygen is the main gas that causes a problem of
deterioration of the content and change of the composition, a resin
with low oxygen permeability is preferable as the gas barrier
resin.
[0284] The gas barrier resin has oxygen permeability, when measured
as a film with a thickness of 20 .mu.m at 23.degree. C. and 0% RH,
of preferably not more than 100
cm.sup.3m.sup.-2day.sup.-1atm.sup.-1, more preferably not more than
50 cm.sup.3m.sup.2day.sup.-1atm.sup.-1, still more preferably not
more than 10 cm.sup.3m.sup.-2day.sup.-1atm.sup.-1, and particularly
preferably not more than 1
cm.sup.3m.sup.-2day.sup.-1atm.sup.-1.
[0285] As the gas barrier resin, a general purpose resin in the
field of packing material and the like can be used. For example, an
ethylene-vinyl alcohol copolymer (EVOH), a vinylidene-chloride
polymer (PVDC), polyesters with barrier properties such as a
polyethylene-isophthalate copolymer, MXD6 nylon (m-xylylene
adipamide), nylon with barrier properties (amorphous nylon),
polyacrylonitrile, liquid-crystal polyester, all-aromatic nylon
(aramid), polyvinyl acetate (PVA) or its hydrolyzate, and the like
can be given. A transparent multilayer film such as PVDC-coated
biaxial stretching polyethylene terephthalate, PVDC-coated
biaxial-stretching polypropylene, and PVDC-coated biaxial
stretching polyvinyl alcohol, a vapor deposition film, and the like
may also be used.
[0286] Of these, an ethylene-vinyl alcohol copolymer (EVOH) is
particularly preferable due to its excellent gas barrier
properties.
[0287] In order to compensate insufficient bending strength, flex
resistance, and tensile strength of the layer made only of the
hydrogenated norbornene ring-open polymer, the multilayer laminate
of the present invention may contain at least one layer of a second
synthetic resin in place of, or in combination with, the layer
containing a gas barrier resin as the synthetic resin.
[0288] Any resin material commonly used for medical application or
food packaging may be used as the resin material forming the second
synthetic resin layer without particular limitations. As examples,
various synthetic resins such as acrylic resins such as a
polyolefin resin, polyamide resin, polyester resin, polymethyl
methacrylate, polycarbonate, ionomer resin, polystyrene, ABS resin,
thermoplastic elastomer, ethylene-carboxylate copolymer,
ethylene-vinyl acetate copolymer, polysulfone, polyvinyl chloride,
and fluororesin can be given. Among these resins, at least one
resin selected from the group consisting of a polyolefin resin, a
polyamide resin, and a polyester resin is preferable.
[0289] As examples of the polyolefin resin, polyethylene resins
such as a linear or branched ethylene-.alpha.-olefin copolymer,
high density polyethylene, low density polyethylene, linear low
density polyethylene, and ultra-high molecular weight polyethylene;
polypropylene resins such as homopolypropylene, ethylene-propylene
random copolymer, ethylene-propylene block copolymer,
ethylene-propylene-1-butene copolymer; polyolefin resins shown by
the group consisting of ethylene-propylene copolymer,
polymethylpentene, polybutene, polymethylbutene, polymethylhexene
and the like; amorphous polyolefin resins such as alicyclic
structure-containing polymers described in JP-A-2001-143323; and
the like can be given.
[0290] As the polyamide resin, nylon 6, nylon 66, nylon 610, nylon
6T, and the like can be given.
[0291] As examples of polyester resin, polyethylene terephthalate,
polybuthylene terephthalate, and polyethylene naphthalate can be
given.
[0292] These synthetic resin layers are used as a monolayer of a
resin or a multilayer laminate of two or more layers. The type of
synthetic resin and the layer constitution can be appropriately
selected according to the purpose of use.
[0293] As the second synthetic resin layer, a layer containing a
polyolefin resin is preferably used, a layer containing
polyethylene or polypropylene is more preferable due to excellent
low elusion properties, chemical resistance, and oil resistance,
and a layer containing polypropylene is particularly preferable due
to excellent heat resistance and transparency in addition to the
above properties.
[0294] The multilayer laminate of the present invention may be
combined with a transparent vapor deposition film in order to
provide gas barrier properties and weather (light) resistance.
[0295] In addition, a metallic foil such as an aluminum foil, an
aluminum vapor deposition film, a laminate film of a metallic foil
and a synthetic resin film, a layer which has a light blocking
effect (shading layer) such as a synthetic resin film with a
pigment incorporated therein may be provided.
[0296] The following combinations of layers can be given as
specific examples of the layer constitution of the multilayer
laminate of the present invention. In the following constitutions,
the layer containing the hydrogenated norbornene ring-open polymer
is indicated as "NB layer" and the other resin layers are indicated
as "synthetic resin layer".
(1) NB layer/synthetic resin layer (2) NB layer/synthetic resin
layer/NB layer (3) Synthetic resin layer/NB layer/synthetic resin
layer (4) NB layer/synthetic resin layer/synthetic resin layer/NB
layer (5) NB layer/synthetic resin layer/NB layer/synthetic resin
layer (6) NB layer/synthetic resin layer/NB layer/synthetic resin
layer/NB layer (7) Synthetic resin layer/synthetic resin layer/NB
layer/synthetic resin layer/synthetic resin layer (8) Synthetic
resin layer/NB layer/synthetic resin layer/NB layer/synthetic resin
layer (9) NB layer/synthetic resin layer/shading layer (10) NB
layer/synthetic resin layer/shading layer/synthetic resin layer
(11) NB layer/shading layer
[0297] The multilayer bodies of the present invention are not
limited to the above combinations. It is possible to employ other
desired multilayer constitutions according to the purpose of use,
such as those having a larger number of layers in addition to any
one of the above layer combinations.
[0298] For example, when the multilayer laminate of the present
invention includes a layer containing a resin having gas barrier
properties, it is necessary for such a resin layer to not come in
contact with water in order to maintain the gas barrier
performance. For this reason, a packing material made from the
multilayer laminate having a gas barrier resin layer of the present
invention is preferably provided with a layer containing the
hydrogenated norbornene ring-open polymer on the side being exposed
to the outside, when it is desired to prevent permeation of
moisture and oxygen from the outside. When the content of the
package is an aqueous solution and the like, it is preferable that
a layer containing the hydrogenated norbornene ring-open polymer be
provided on the side being exposed to the content of the
package.
[0299] In the multilayer laminate of the present invention, an
adhesive layer consisting of an intercalation adhesive may be
optionally provided between the layers.
[0300] There are no particular limitations to the intercalation
adhesive insofar as the adhesive does not adversely affect the film
properties. As examples, an adhesive rubber, an adhesive
thermoplastic resin, an adhesive thermoplastic elastomer,
thermosetting adhesives such as an epoxy resin, a silicone resin,
and an urethane resin, thermoplastic adhesives such as polyvinyl
ether, an acrylic resin, and a vinyl acetate-ethylene copolymer, a
hotmelt polyamide resin adhesive, rubber adhesives such as nitrile
rubber, and the like may be given. Among these, a urethane adhesive
and an adhesive olefin polymer are preferable.
[0301] The synthetic resin layer of the multilayer laminate of the
present invention may contain an additive which may be used with
the hydrogenated norbornene ring-open polymer.
[0302] The multilayer laminate of the present invention may be
obtained by molding the hydrogenated ring-open polymer of the
present invention or a resin composition containing the
hydrogenated ring-open polymer of the present invention and
additives, and a resin used for the synthetic resin layer or a
resin composition containing the resin used for the synthetic resin
layer and additives by a known molding method.
[0303] Although not particularly limited, the method of molding the
multilayer laminate of the present invention includes, for example,
a coextrusion molding method such as a coextrusion T-die method, a
coextrusion inflation method, and a coextrusion lamination method;
film lamination molding methods such as dry lamination; a coating
mold method in which a resin solution is applied to a substrate
resin film, a calendar molding method, a heat press molding method,
an injection molding method, and the like.
[0304] The molding conditions are suitably selected according to
the type of the resin used.
[0305] There are no particular limitations to the shape of the
multilayer laminate of the present invention. When used as a
packing material, the multilayer laminate may usually be in the
form of a film or a sheet, but may be in the form of a tube.
[0306] The multilayer laminate of the present invention may usually
be unstretched, but may be stretched as required.
[0307] The stretching may be carried out by any method such as a
roll method, a tenter method, and a tube method. The stretching
conditions are suitably selected according to the type of the resin
used.
[0308] Although there are no specific limitations, the thickness of
the multilayer laminate of the present invention obtained by the
above-mentioned method is usually 5 to 1000 .mu.m, preferably 20 to
500 .mu.m, and more preferably 30 to 300 .mu.m. If the thickness is
more than the above maximum thickness, the multilayer laminate does
not have pliability; if the thickness is less than the above
minimum thickness, the multilayer laminate has insufficient
strength and tends to be ruptured easily.
[0309] Printing may be applied to the multilayer laminate of the
present invention.
[0310] A common printing method such as letterpress printing, hand
gravure printing, and surface printing may be used without
particular limitation. A suitable printing ink may be appropriately
selected according to the printing method. For example, a
letterpress ink, a flexographic ink, a dry offset ink, a
photogravure ink, a photogravure offset ink, an offset ink, and a
screen ink may be given.
[0311] In order to improve adhesion of the ink, it is preferable to
apply a surface treatment to the printing layer before applying a
printing ink. As the method of surface treatment, a corona
discharge treatment, a plasma discharge treatment, a flame
treatment, an emboss processing treatment, a sand mat processing
treatment, a satin processing treatment, and the like can be
given.
[0312] The multilayer laminate of the present invention is
excellent also in impact resistance. The impact resistance may be
confirmed by layering two sheets of the multilayer laminate with a
thickness of 50 .mu.m, preparing a 20 cm.times.20 cm bag by sealing
the sides with heat, putting brine in the bag, and dropping the bag
from a height of 3 m. The presence or absence of cracks immediately
after dropping is determined with the naked eye. Excellent impact
resistance can be confirmed if there are almost no cracks
observed.
[0313] The multi layer laminate of the present invention has
excellent steam barrier properties. The moisture permeability of
the multilayer laminate with a thickness of 50 .mu.m of the present
invention is usually 3 g/(m.sup.224 h) or less, preferably 2.5
g/(m.sup.224 h) or less.
[0314] The steam barrier properties can be measured according to
JIS K7129 (method A), for example, using a moisture permeability
tester (L80-5000 type, manufactured by LYSSY) under the conditions
of a temperature of 50.degree. C. and humidity of 90% RH.
[0315] The multilayer laminate having at least one layer containing
a gas barrier resin has excellent gas barrier properties. The
oxygen permeability of the multilayer laminate having at least one
layer containing a gas barrier resin with a thickness of 50 of the
present invention is usually 0.5
cm.sup.3m.sup.-2day.sup.-1atm.sup.-1 or less, and preferably 0.35
cm.sup.3m.sup.-2day.sup.-1atm.sup.-1 or less.
[0316] The multilayer laminate having at least one layer containing
a gas barrier resin shows almost no decrease in the oxygen
permeability after having been left under high temperature and high
humidity conditions (e.g. after having been left in boiling water
for 30 minutes).
[0317] The gas barrier properties of the multilayer laminate can be
evaluated by dipping a bag made of the multilayer laminate of the
present invention in boiling water for 30 minutes and measuring the
gas barrier properties before and after boiling according to JIS
K7126 (method B) under the conditions of a temperature of
23.degree. C. and humidity of 0% RH using an oxygen permeability
tester (OPT-5000 type, manufactured by LYSSY), for example.
[0318] The multilayer laminate of the present invention is
excellent in oil resistance. The oil resistance can be evaluated by
cutting a 5 cm square from the film to obtain a sample, dipping the
sample in salad oil (manufactured by Nisshin Oillio Group, Ltd.)
for 30 seconds, and placing the sample in an oven heated at
40.degree. C., and measuring the period of time elapsed before the
outward appearance of the sample changes. The oil resistance of the
multilayer laminate of the present invention is indicated by the
number of days before the film is whitened, which is usually four
days, preferably five days, and more preferably six days.
[0319] The fields in which the multilayer laminate of the present
invention is particularly useful include, in addition to the fields
of foods, medical supplies, displays, energy, and other industrial
fields, wrapping materials for toys, household goods, and the like.
A packing material with a desired shape and size may be prepared by
secondary fabrication of the multilayer laminate of the present
invention as mentioned later.
[0320] Due to possession of excellent steam barrier properties and
impact resistance, the multilayer laminate of the present invention
is suitably used for applications requiring hot water
sterilization, retorting, hot filling, steam sterilization, and the
like. When at least one layer contains a gas barrier resin, the
multilayer laminate of the present invention exhibits only a small
change in the gas barrier properties under high temperature and
high humidity conditions. For example, medical-related containers
or films for packing bags such as an infusion solution bag, PTP
(press-through package), and a syringe; films for a food container
or a packing bag and a blister pack such as a retort pack requiring
heat sterilization, a jelly or pudding container, a container for
processed foods such as ham, sausage, and frozen food, containers
for dried food, specified health food, rice, confectionery, and
meat, as well as lids for these containers, and hot-fill
containers; a film and a blister pack for packaging containers or
packing bag for precision components such as electric and
electronic parts, semiconductor parts, and printed circuit boards;
a heat-shrinkable film and blister pack of packing material for
storing and transporting foods, medicines, instruments,
miscellaneous goods such as stationery supplies and notebooks; a
film and a blister pack for tamper-resistant seal packing materials
such as a cap and a plug; a film for heat-shrinkable label material
for containers, solar energy power generation system components,
fuel cell components, and alcohol-containing fuel system
components, as well as films and blisters for these components; and
the like can be given.
6) Packing Material
[0321] The packing material of the present invention is obtained by
secondary fabrication of the multilayer laminate of the present
invention.
[0322] There are no particular limitations to the method of
secondary fabrication. Press molding, vacuum molding, air-pressure
forming, heat-sealing, and melt bonding can be given as
examples.
[0323] As the manner of heat-sealing, the innermost layer of the
multilayer laminate is folded or two multilayer bodies are layered
and the periphery of the circumference is heat-sealed by side
sealing, two-way sealing, three-way sealing, four-way sealing,
envelope sealing, pillow sealing, diaphragm sealing, flat bottom
sealing, cornered bottom sealing, or the like.
[0324] Various generally known heat-sealing methods may be employed
without particular limitations. A bar seal method, a rotation roll
seal method, a belt seal method, an impulse sealing method, a high
frequency seal method, and an ultrasonic seal method can be given
as examples. The packing material may be provided with a
one-piece-type or two-piece-type injection port, a zipper for
opening and closing, and the like.
[0325] As a blister molding method for fabricating a pocket, an
appropriate method such as heat-press forming, drum vacuum forming,
plug die forming, pin molding, preheater pressure forming,
preheater plug-assist pressure forming, and the like may be used. A
pocket with a shape such as a cylinder, a dome, an ellipse dome and
a size conforming to the object to be contained may be prepared by
the blister molding.
[0326] The packing material of the present invention has excellent
steam barrier properties, mechanical properties such as impact
resistance, and oil resistance, and when possessing at least one
layer containing a gas barrier resin, has excellent gas barrier
properties in a high temperature and high humidity environment.
Therefore, the packing material is suitable for a medical supply
packing container, a food packing container, and the like.
7) Medical Supply Packing Material
[0327] The medical supply packing material of the present invention
has at least one resin layer of a layer of a hydrogenated
norbornene ring-open polymer obtained by hydrogenating 80% or more
of carbon-carbon double bonds of a ring-open polymer which is
obtained by ring-opening polymerization of 2-norbornene and a
substituent-containing norbornene monomer, the proportion of a
repeating unit (A) derived from the 2-norbornene with respect to
all repeating units being 90 to 100 wt % and the proportion of a
repeating unit (B) derived from the substituent-containing
norbornene monomer with respect to all repeating units being 0 to
10 wt %, and the hydrogenated norbornene ring-open polymer having a
melting point of 110 to 145.degree. C.
[0328] Specifically, the hydrogenated norbornene ring-open polymer
used as the medical supply packing material of the present
invention is the same as the hydrogenated norbornene ring-open
polymer of the present invention described above, except that
weight average molecular weight (Mw) determined by gel permeation
chromatography (GPC) or the molecular weight distribution (Mw/Mn)
of hydrogenated norbornene ring-open polymer may not be
particularly limited, when such a polymer is obtained by
hydrogenating 80% or more of main-chain carbon-carbon double bonds
of a ring-open polymer which is obtained by ring-opening
polymerization of 2-norbornene (hydrogenated 2-norbornene ring-open
polymer). The polymers mentioned above as preferable examples of
the hydrogenated norbornene ring-open polymer of the present
invention are preferable hydrogenated norbornene ring-open polymers
used as the medical supply packing material of the present
invention.
[0329] The monomer mixture used for producing the hydrogenated
norbornene ring-open polymer used for the medical supply packing
material of the present invention comprises usually 90 to 100 wt %,
preferably 95 to 99 wt %, and more preferably 97 to 99 wt % of
2-norbornene and usually 0 to 10 wt %, preferably 1 to 5 wt %, and
more preferably 1 to 3 wt % of the substituent-containing
norbornene monomers.
[0330] The proportion of the repeating unit (A) derived from
2-norbornene with respect to all repeating units of the
hydrogenated norbornene ring-open polymer used for the medical
supply packing material of the present invention is 90 to 100 wt %,
preferably 95 to 99 wt %, and more preferably 97 to 99 wt %, and
the proportion of the repeating unit (B) derived from the
substituent-containing norbornene monomer with respect to all
repeating units of the hydrogenated norbornene ring-open polymer is
0 to 10 wt %, preferably 1 to 5 wt %, and more preferably 1 to 3 wt
%.
[0331] Various additives may be added to the hydrogenated
norbornene ring-open polymer used for the medical supply packing
material of the present invention according to the purpose of
application. Examples of the additives include antioxidants,
rubber-like polymers and other resins, UV absorbers,
weather-resistant stabilizers, antistatic agents, slipping agents,
anticlouding agents, dyes, pigments, coloring agents, natural oils,
synthetic oils, plasticizers, organic or inorganic fillers,
antibacterial agents, deodorants, and the like. As specific
examples of the additives used for the medical supply packing
material of the present invention, the same additives as those used
for the multilayer laminate of the present invention may be given.
As specific examples of the additives preferably used for the
medical supply packing material of the present invention, the same
additives as those preferably used for the multilayer laminate of
the present invention may be given.
[0332] The medical supply packing material of the present invention
may be made of only a resin layer containing the hydrogenated
ring-open polymer of the present invention or made of a multilayer
laminate which contains, in addition to at least one resin layer
containing the hydrogenated norbornene ring-open polymer of the
present invention, a synthetic resin layer which contains at least
one other layer.
[0333] The medical supply packing material of the multilayer
laminate is preferable due to increased oil resistance, pliability,
impact resistance, heat resistance, and the like.
[0334] The content of the hydrogenated ring-open polymer in the
resin layer which contains the hydrogenated ring-open polymer in
the medical supply packing material of the present invention is
usually 50 to 100 wt %, preferably 70 to 100 wt %, and more
preferably 90 to 100 wt %. The content of the hydrogenated
ring-open polymer in this range is preferable because the
characteristics possessed by the hydrogenated ring-open polymer
such as steam barrier properties are not impaired.
[0335] Although there are no specific limitations, the thickness of
the layer containing the hydrogenated ring-open polymer is usually
1 to 500 .mu.m, preferably 10 to 150 .mu.m, and more preferably 20
to 100 .mu.m. This thickness range is preferable because the
characteristics possessed by the hydrogenated ring-open polymer
such as steam barrier properties are not impaired.
[0336] Any resins that are used for medical applications may be
used as the other resins without a particular limitation. Examples
include various synthetic resins such as a polyolefin resin,
polyethylene terephthalate, polybuthylene terephthalate,
polymethylmethacrylate, polycarbonate, ionomer resin, polystyrene,
ABS resin, thermoplastic elastomer, nylon, ethylene-vinyl acetate
copolymer, ethylene-vinyl alcohol copolymer (EVOH), nylon,
polysulfone, and the like.
[0337] Among these resins, the polyolefin resin is particularly
preferable because of its effect of improving mechanical
properties, oil resistance, and the like of the medical supply
packing material.
[0338] As examples of the polyolefin resin, polyolefin crystalline
resins shown by the group consisting of polyethylene resins such as
a linear or branched high density polyethylene, low density
polyethylene, and ultra-high molecular weight polyethylene;
polypropylene resins such as linear or branched high density
polypropyrene and low density polypropyrene; ethylene-propylene
copolymer, polymethylpentene, polybutene, polymethylbutene, and
polymethylhexene; and the like can be given.
[0339] Among these, the polyethylene-containing synthetic resin
layer is preferably used for fabricating multilayer laminate. The
multilayer laminate obtained by using such a synthetic resin layer
exhibits excellent low elusion properties, oil resistance, and
chemical resistance. Furthermore, low density polyethylene, which
has a density of 0.88 to 0.94 g/cm.sup.3 measured according to JIS
K6922, has superior transparency in addition to these excellent
properties.
[0340] In addition, a gas barrier resin such as an ethylene-vinyl
alcohol copolymer, nylon, or the like is preferable as a layer to
be laminated to promote the gas barrier properties of the resulting
multilayer laminate.
[0341] In the medical supply packing material of the present
invention, in addition to the resin layer containing the
hydrogenated ring-open polymer and the synthetic resin layer
containing the other resins, a metallic foil such as an aluminum
foil, an aluminum vapor deposition film, a laminate film of a
metallic foil and a synthetic resin film, a layer which has a light
blocking effect (shading layer) such as a synthetic resin film with
a pigment incorporated therein may be provided.
[0342] There are no particular limitations to the constitution of
the multilayer laminate used for the medical supply packing
material of the present invention inasmuch as such a multilayer
laminate contains at least the resin layer containing the
hydrogenated ring-open polymer and the synthetic resin layer
containing the other resins. As specific examples, the following
combinations of layers can be given. In the following
constitutions, the resin layer containing the hydrogenated
ring-open polymer is indicated as "NB layer" and the synthetic
resin layers containing the other resin are indicated as "synthetic
resin layer".
(1) NB layer/synthetic resin layer (2) NB layer/synthetic resin
layer/NB layer (3) Synthetic resin layer/NB layer/synthetic resin
layer (4) NB layer/synthetic resin layer/synthetic resin layer/NB
layer (5) NB layer/synthetic resin layer/NB layer/synthetic resin
layer (6) NB layer/synthetic resin layer/NB layer/synthetic resin
layer/NB layer (7) Synthetic resin layer/synthetic resin layer/NB
layer/synthetic resin layer/synthetic resin layer (8) Synthetic
resin layer/NB layer/synthetic resin layer/NB layer/synthetic resin
layer (9) NB layer/synthetic resin layer/shading layer (10) NB
layer/synthetic resin layer/shading layer/synthetic resin layer
(11) NB layer/shading layer
[0343] It is possible to employ other desired multilayer
constitutions according to the purpose of use, such as those having
a larger number of layers in addition to any one of the above layer
combinations.
[0344] In the medical supply packing material of the present
invention, an adhesive layer may be optionally provided between the
layers.
[0345] As the adhesive, the same adhesives that are given as the
adhesive to be used in the multilayer laminate can be given.
[0346] In the synthetic resin layer of the medical supply packing
material of the present invention, the synthetic resin layer which
contains the other resins may contain additives which may be used
with the hydrogenated norbornene ring-open polymer.
[0347] When the medical supply packing material of the present
invention is a monolayer material, such a monolayer material may be
obtained by molding the hydrogenated ring-open polymer of the
present invention or a resin composition containing the
hydrogenated ring-open polymer and additives (hereinafter may be
referred to from time to time as "resin composition (1)") by a
known molding method.
[0348] As an example of the method for preparing the resin
composition (1), a method of melt-kneading the hydrogenated
ring-open polymer and the additives using a twin-screw kneader, for
example, at 200 to 400.degree. C., and producing pellets, granules,
or powder from the kneaded product can be given.
[0349] There are no particular limitations to the method of molding
the hydrogenated ring-open polymer or the resin composition (1).
Generally known methods, for example, the molding method such as a
T-die method, an inflation method, or a lamination method; the film
lamination mold method such as dry lamination; heat-press molding
method; injection molding method; and the like may be appropriately
used. The molding conditions are suitably selected according to the
type of the resin used.
[0350] When the medical supply packing material of the present
invention is a multilayer material, such a multilayer material may
be obtained by molding the hydrogenated ring-open polymer or the
resin composition (1) and a resin composition containing the other
resin and other additives (hereinafter may be referred to from time
to time as "resin composition (2)") by a known molding method.
[0351] The resin composition (2) may be prepared in the same manner
as the resin composition (1).
[0352] In the present invention, the molded article may be annealed
in order to increase crystallinity.
[0353] In order to increase the mechanical properties and steam
barrier properties, the medical supply packing material may be
stretched to increase the crystallinity. This is an operation of
applying plastic deformation to a sheet or film by stretching the
length of the molded film or sheet 1.1 to 10 times. The plastic
deformation has an effect of orienting amorphous chains, not to
mention of crystalline chains, by internal friction caused by
stretching.
[0354] The medical supply packing material of the present invention
may be usually a film or a sheet, but may be a tube. If processed
by an inflation method, the product has a form of a tube (a
cylinder). A bag can be prepared by a simple process of cutting the
tube and sealing one open side. When the inflation method is used,
it is preferable to have a die lip clearance of 2.5 mm or more in
order to prevent melt flow fracture due to the shearing stress when
the resin is extruded at a high speed (8 m/min or more).
[0355] In this instance, the molding temperature in terms of the
die temperature is preferably 180 to 210.degree. C. If the die
temperature is 210.degree. C. or higher, burning (discoloration)
and fish eyes tend to occur easily and film formation (molding)
becomes difficult due to a decrease of melt viscosity. The screw
compression ratio is preferably not more than 3.0. If the screw
compression ratio is more than 3.0, self-heating may increase and
molding will become difficult.
[0356] Although there are no specific limitations, the thickness of
the medical supply packing material obtained in the manner as
described above is usually 100 to 500 .mu.m, preferably 150 to 350
.mu.m, and still more preferably 200 to 300 .mu.m. If the thickness
of the packing material is more than the above maximum thickness,
the film does not have pliability; if the thickness is less than
the above minimum thickness, the medical supply packing material
has insufficient strength and tends to rupture easily.
[0357] The medical supply packing material of the present invention
may be obtained by molding the hydrogenated ring-open polymer or
the resin composition (1) or the hydrogenated ring-open polymer or
the resin composition (1) and the other resin or the resin
composition (2) into a film or a sheet and subjecting the film or
the sheet to secondary processing.
[0358] Although not particularly limited, press molding, vacuum
molding, pressure forming, heat-sealing, and melt bonding can be
given as examples of the secondary processing. Of these,
heat-sealing is preferable.
[0359] As the manner of heat-sealing, the innermost layer of the
multilayer films or multilayer sheets is folded or two multilayer
sheets or films are layered and the periphery of the circumference
is heat-sealed by side sealing, two-way sealing, three-way sealing,
four-way sealing, envelope sealing, pillow sealing, diaphragm
sealing, flat bottom sealing, cornered bottom sealing, or the
like.
[0360] Various generally known heat-sealing methods may be employed
without particular limitation. A bar seal method, a rotation roll
seal method, a belt seal method, an impulse sealing method, a high
frequency seal method, and an ultrasonic seal method can be given
as examples. The packaging material may be provided with a
one-piece-type or two-piece-type injection port, a zipper for
opening and closing, and the like.
[0361] The medical supply packing material of the present invention
obtained in the above-described manner only has small unevenness in
the film thickness. If unevenness of the film thickness is large
and the thickness varies in different areas of the film, the
rolled-up film contains hard swollen portions (lumps) which cause a
problem during printing or heat-sealing.
[0362] An uneven film thickness of the medical supply packing
material of the present invention can be evaluated by, for example,
applying five marks on the film at 4 cm intervals in the direction
(TD direction) vertical to the flow direction of the film, applying
20 marks at 20 cm intervals in the flow direction (MD direction) of
the film starting from the first five marks, thereby applying 100
marks in total, and measuring the film thickness at the 100-mark
points. The smaller the value of the standard deviation calculated
from the thickness measurement result, the smaller the thickness
unevenness. In the medical supply packing material of the present
invention, the standard deviation of a film with a thickness of 250
.mu.m is not more than 10 .mu.m.
[0363] The medical supply packing material of the present invention
obtained in this manner has excellent steam barrier properties. The
medical supply packing material of the present invention with a
thickness of 250 .mu.m has moisture permeability measured based on
JIS K7129 (Method A) at a temperature of 50.degree. C. at 90% RH of
usually 2 g/(m.sup.224 h) or less, preferably 1.5 g/(m.sup.224 h)
or less, and more preferably 1 g/(m.sup.224 h) or less. If the
moisture permeability is within this range, mixing of moisture into
the medicine packed in the medical supply packing material is
suppressed and quality deterioration of the drug can be
prevented.
[0364] The medical supply packing material of the present invention
has an excellent modulus of elasticity. It is desirable that
modulus of elasticity of a sample of the medical supply packing
material of the present invention having an IB shape and a
thickness of 250 .mu.m measured according to ISO 527 at a tensile
velocity of 200 mm/min using Autograph (AGS-5kNH, manufactured by
Shimadzu Corp.) is not more than 500 MPa. If the modulus of
elasticity is not more than 500 MPa, the medical supply packing
material has excellent pliability and can transfer a medical fluid
at a uniform flow rate when used as an infusion solution bag. If
the modulus of elasticity is more than 500 MPa, on the other hand,
the infusion solution bag is hard and it is difficult to transfer a
medical fluid at a uniform flow rate.
[0365] The medical supply packing material of the present invention
also has excellent oil resistance. When the oil resistance
evaluation value (haze of untreated sample/haze after applying
salad oil) is 0.8 or more, the medical supply packing material is
resistant to oil and has its appearance or performance impaired
only with difficulty when oil is attached to the surface.
[0366] The medical supply packing material of the present invention
has excellent mechanical properties. Distortion of the medical
supply packing material of the present invention at the time of a
surface crack measured using a sample having an IB shape and a
thickness of 250 .mu.m according to ISO 527 at a tensile velocity
of 200 mm/min using Autograph (AGS-5kNH, manufactured by Shimadzu
Corp.) is usually 20% or more, preferably 25% or more, and more
preferably 30% or more. When the distortion is within this range,
cracks and ruptures occur only with difficulty in the medical
supply packing material.
[0367] As specific examples of the medical supply packing material,
a medical-related container such as an infusion solution bag and a
PTP (press through package); a film or a sheet for packing a
syringe; and the like can be given. An infusion solution bag is the
particularly preferable application.
8) Blister Molding Sheet
[0368] The blister molding sheet of the present invention has at
least one layer of a resin which is obtained by hydrogenating 80%
or more of carbon-carbon double bonds of a ring-open polymer
obtained by ring-opening polymerization of 2-norbornene or a
monomer mixture of 2-norbornene and a substituent-containing
norbornene monomer, the proportion of a repeating unit (A) derived
from the 2-norbornene with respect to all repeating units being 90
to 100 wt % and the proportion of a repeating unit (B) derived from
the substituent-containing norbornene monomer in all repeating unit
being 0 to 10 wt %, and the hydrogenated norbornene ring-open
polymer having a melting point of 110 to 145.degree. C.
[0369] Specifically, the hydrogenated norbornene ring-open polymer
used as the blister molding sheet of the present invention is the
same as the hydrogenated norbornene ring-open polymer of the
present invention described above, except that the weight average
molecular weight (Mw) determined by gel permeation chromatography
(GPC) or the molecular weight distribution (Mw/Mn) of the
hydrogenated norbornene ring-open polymer may not be particularly
limited if such a polymer is obtained by hydrogenating 80% or more
of main-chain carbon-carbon double bonds of a ring-open polymer
which is obtained by ring-opening polymerization of 2-norbornene
(hydrogenated 2-norbornene ring-open polymer). The polymers
mentioned above as preferable examples of the hydrogenated
norbornene ring-open polymer of the present invention are
preferable hydrogenated norbornene ring-open polymers used as the
blister molding sheet of the present invention.
[0370] The monomer mixture used for producing the hydrogenated
norbornene ring-open polymer used for the blister molding sheet of
the present invention comprises usually 90 to 100 wt %, preferably
95 to 99 wt %, and more preferably 97 to 99 wt % of 2-norbornene
and usually 0 to 10 wt %, preferably 1 to 5 wt %, and more
preferably 1 to 3 wt % of substituent-containing norbornene
monomers.
[0371] The proportion of the repeating unit (A) derived from
2-norbornene with respect to all repeating units of the
hydrogenated norbornene ring-open polymer used for the blister
molding sheet of the present invention is usually 90 to 100 wt %,
preferably 95 to 99 wt %, and more preferably 97 to 99 wt %, and
the proportion of the repeating unit (B) derived from the
substituent-containing norbornene monomer with respect to all
repeating units of the hydrogenated norbornene ring-open polymer is
0 to 10 wt %, preferably 1 to 5 wt %, and more preferably 1 to 3 wt
%.
[0372] Various additives may be added to the hydrogenated
norbornene ring-open polymer used for the blister molding sheet of
the present invention according to the purpose of application.
Examples of the additives include antioxidants, rubber-like
polymers and other resins, UV absorbers, weather-resistant
stabilizers, antistatic agents, slipping agents, anticlouding
agents, dyes, pigments, coloring agents, natural oils, synthetic
oils, plasticizers, organic or inorganic fillers, antibacterial
agents, deodorants, and the like. As specific examples of the
additives used for the blister molding sheet of the present
invention, the same additives as those used for the multilayer
laminate of the present invention may be given. As specific
examples of the additives preferably used for the medical supply
packing material of the present invention, the same additives as
those preferably used for the multilayer laminate of the present
invention may be given.
[0373] The blister molding sheet of the present invention has at
least one resin layer containing the hydrogenated ring-open polymer
of the present invention. The blister molding sheet of the present
invention may consist only of a layer containing the hydrogenated
ring-open polymer or may be a multilayer laminate further
comprising at least one synthetic resin layer containing another
resin.
[0374] The content of the hydrogenated ring-open polymer in the
resin layer which contains the hydrogenated ring-open polymer in
the blister molding sheet of the present invention is usually 50 to
100 wt %, preferably 70 to 100 wt %, and more preferably 90 to 100
wt %. The content in this range is preferable because the
characteristics possessed by the hydrogenated ring-open polymer
such as steam barrier properties are not impaired.
[0375] Although there are no specific limitations, the thickness of
the layer containing the hydrogenated norbornene ring-open polymer
is usually 5 to 1000 .mu.m, preferably 5 to 500 .mu.m, more
preferably 10 to 300 .mu.m, and still more preferably 20 to 200
.mu.m. The thickness in the above range is preferable because the
characteristics possessed by the hydrogenated ring-open polymer
such as steam barrier properties are not impaired.
[0376] Any resin material commonly used for packing foods, medical
supplies, industrial parts, and the like may be used as the other
resins. As examples, various synthetic resins such as a polyolefin
resin, polyethylene terephthalate, polybuthylene terephthalate,
polymethyl methacrylate, polycarbonate, ionomer resin, polystyrene,
ABS resin, thermoplastic elastomer, nylon, ethylene-carboxylate
copolymer, ethylene-carboxylic acid copolymer, ethylene-vinyl
acetate copolymer, ethylene-vinyl alcohol copolymer (EVOH), nylon,
polysulfone, polyvinyl chloride, polyvinylidene chloride, and
fluororesin can be given.
[0377] These synthetic resin layers are used as a monolayer of a
resin or a multilayer laminate of two or more layers. The type of
the synthetic resin and the layer constitution can be appropriately
selected according to the purpose of use.
[0378] The blister molding sheet of a multilayer laminate is
preferable due to increased mechanical properties, oil resistance,
blister moldability, and the like. Among the above synthetic resin
layers, a synthetic resin layer containing a polyolefin resin layer
or a layer containing a gas barrier resin such as an ethylene-vinyl
alcohol copolymer, nylon, or a polyvinylidene chloride as another
layer is preferable.
[0379] As examples of the polyolefin resin, polyolefin-based
crystalline resins shown by the group consisting of a linear or
branched ethylene-.alpha.-olefin copolymer, polyethylene resins
such as high density polyethylene, low density polyethylene, linear
low density polyethylene, and ultra-high molecular weight
polyethylene; polypropylene resins such as homopolypropylene, an
ethylene-propylene random copolymer, an ethylene-propylene block
copolymer, and an ethylene-propylene-1-butene copolymer; an
ethylene propylene copolymer, polymethylpentene, polybutene,
polymethylbutene, polymethylhexene and the like; alicyclic
structure-containing polymer resins such as a norbornene polymer, a
monocycle cycloolefin polymer, a cyclic conjugated diene polymer, a
vinyl alicyclic hydrocarbon polymer, and hydrogenated products of
these polymers described in JP-A-2001-143323; and the like can be
given.
[0380] Among these, the synthetic resin layer containing
polyethylene or polypropylene is more preferable due to excellent
low elusion properties, chemical resistance, and oil resistance,
and a layer containing polypropylene is particularly preferable due
to excellent heat resistance and transparency in addition to the
above properties.
[0381] In addition, a layer containing a gas barrier resin as the
synthetic resin layer containing other resins is preferable to
improve gas barrier properties.
[0382] The blister molding sheet of the present invention may be
combined with a transparent vapor deposition film in order to
provide gas barrier properties and weather (light) resistance.
[0383] In addition, the blister molding sheet of the present
invention may be provided with a metallic foil such as an aluminum
foil, an aluminum vapor deposition film, a laminate of a metallic
foil and a synthetic resin film, a layer which has a light blocking
effect (shading layer) such as a synthetic resin film with a
pigment incorporated therein.
[0384] The synthetic resin layer and the shading layer of the
blister molding sheet of the present invention may be a laminate of
two or more layers.
[0385] It is possible to employ a desired multilayer constitution
according to the purpose of use of the blister molding sheet. There
are no particular limitations to the constitution of the multilayer
laminate used for the blister molding sheet of the present
invention inasmuch as such a multilayer laminate contains a layer
of the hydrogenated ring-open polymer of the present invention and
a layer of the other material. In the following constitutions, the
resin layer containing the hydrogenated ring-open polymer is
indicated as "NB layer" and the synthetic resin layers containing
the other resin are indicated as "synthetic resin layer".
(1) NB layer/synthetic resin layer (2) NB layer/synthetic resin
layer/NB layer (3) Synthetic resin layer/NB layer/synthetic resin
layer (4) NB layer/synthetic resin layer/synthetic resin layer/NB
layer (5) NB layer/synthetic resin layer/NB layer/synthetic resin
layer (6) NB layer/synthetic resin layer/NB layer/synthetic resin
layer/NB layer (7) Synthetic resin layer/synthetic resin layer/NB
layer/synthetic resin layer/synthetic resin layer (8) Synthetic
resin layer/NB layer/synthetic resin layer/NB layer/synthetic resin
layer (9) NB layer/synthetic resin layer/shading layer (10) NB
layer/synthetic resin layer/shading layer/synthetic resin layer
(11) NB layer/shading layer
[0386] In the blister molding sheet of the present invention, an
adhesive layer may be optionally provided between the layers.
[0387] As specific examples of the adhesive which forms the
adhesive layer, an adhesive rubber, an adhesive thermoplastic
resin, an adhesive thermoplastic elastomer, thermosetting adhesives
such as an epoxy resin, a silicone resin, and a urethane resin,
thermoplastic adhesives such as polyvinyl ether, an acrylic resin,
and a vinyl acetate-ethylene copolymer, a hotmelt polyamide resin
adhesive, rubber adhesives such as nitrile rubber, and the like may
be given. Although there are no specific limitations to the extent
that the properties of the film are not affected, a urethane
adhesive and an adhesive olefin polymer are preferable among these
adhesives.
[0388] The synthetic resin layer of the blister molding sheet of
the present invention may contain an additive which may be used
with the hydrogenated norbornene ring-open polymer.
[0389] The method for molding the blister molding sheet of the
present invention includes, for example, molding methods such as a
T-die method, an inflation method, and a coextrusion T-die method,
a coextrusion inflation method, a coextrusion lamination method;
film lamination molding methods such as dry lamination; a coating
mold method in which a resin solution is applied to a substrate
resin film, a calendar molding method, a heat press molding method,
an injection molding method, and the like.
[0390] The molding conditions are suitably selected according to
the type of the resin used.
[0391] The blister molding sheet of the present invention may be
usually unstretched, but may be stretched as required. Stretching
can increase the degree of crystallization, mechanical properties,
and steam barrier properties.
[0392] The stretching may be carried out by any method such as a
roll method, a tenter method, and a tube method. Although the
stretching conditions are suitably selected according to the type
of the sheet used, the sheet is usually stretched about 1.1 to 10
times.
[0393] The blister molding sheet of the present invention obtained
by the above-mentioned method has a thickness of usually 5 to 1000
.mu.m, preferably 10 to 500 .mu.m, more preferably 30 to 400 .mu.m,
and still more preferably 40 to 300 .mu.m. If the thickness of the
blister molding sheet is more than the above maximum thickness, the
sheet does not have pliability; if the thickness is less than the
above minimum thickness, the blister molding sheet has insufficient
strength and tends to rupture.
[0394] As desired, printing may be applied to the blister molding
sheet of the present invention.
[0395] A common printing method such as letterpress printing, hand
gravure printing, and surface printing may be used without a
particular limitation. A suitable printing ink may be appropriately
selected according to the printing method. For example, a
letterpress ink, a flexographic ink, a dry offset ink, a
photogravure ink, a photogravure offset ink, an offset ink, and a
screen ink may be given.
[0396] In order to improve adhesion of the ink, it is preferable to
apply a surface treatment to the printing layer before applying a
printing ink. As the method of surface treatment, a corona
discharge treatment, a plasma discharge treatment, a flame
treatment, an emboss processing treatment, a sand mat processing
treatment, a satin processing treatment, and the like can be
given.
[0397] The fields in which the blister molding sheet of the present
invention is particularly useful include, in addition to the fields
of food industries, medical supplies, displays, energy, and other
industrial fields, toys, household goods, and the like. Since the
blister molding sheet does not produce a thickness variation during
blister molding, has excellent mechanical strength, and
particularly exhibits only a minimal change in the steam barrier
properties according to the change in environment, the blister
molding sheet is suitable for packing goods to be preserved for a
long period of time under natural environmental conditions. For
example, the blister molding sheet is suitable for use as a
container or a blister pack for medical supplies such as a press
through package (PTP), a syringe, and the like; foods; precision
components such as electric and electronic parts, semiconductor
parts, printed circuit boards; solar energy power generation system
components; fuel cell components; alcohol-containing fuel system
components; and the like.
9) Blister Molded Article
[0398] The blister molded article of the present invention is
obtained by forming the blister molding sheet of the present
invention.
[0399] Specifically, a blister molded article may be obtained by
forming the blister molding sheet by a commonly known method to
batch-wisely or continuously prepare plastic sheets having one or
more concave portions (pockets) to store goods therein (blister
molding) and, as required, folding two sides or three sides among
the left, right, top and bottom sides with heating (sheet
processing) to form cuff parts for inserting substrates or mat
boards so that the concave portions may be blocked.
[0400] There are no specific limitations to the blister molding
method for forming the pockets. For example, (i) a flat board blow
molding method of softening the blister molding sheet of the
present invention with heat, putting the softened sheet between a
lower mold which has a hole to which a high pressure air is
supplied and an upper mold which has a pocket-shaped recess, and
feeding air to form pockets, (ii) a drum vacuum molding method of
softening the blister molding sheet of the present invention with
heat and drawing a pocket-shaped recessed portion of a drum having
the recessed portion to form pockets, (iii) a plug molding method
of softening a pocket-shaped concavo-convex die and
pressure-bonding the blister molding sheet of the present
invention, and (iv) a plug assist blow molding method of assisting
the operation of blow molding in the method (i) by elevating and
then moving a convex-shaped plug downward can be given.
[0401] The molding conditions are suitably selected according to
the type of the blister molding sheet used.
[0402] Although there are no particular limitations, heat-sealing,
melt bonding, and the like can be given as the method of sheet
processing after blister molding.
[0403] Various generally known heat-sealing methods may be employed
without particular limitation. A bar seal method, a rotation roll
seal method, a belt seal method, an impulse sealing method, a high
frequency seal method, and an ultrasonic seal method can be given
as examples.
[0404] The blister molded article may be provided with a
one-piece-type or two-piece-type injection port, a zipper for
opening and closing, and the like.
[0405] The blister molded article of the present invention obtained
in this manner has excellent steam barrier properties. The blister
molded sheet of the present invention with a thickness of 250 .mu.m
has moisture permeability at 50.degree. C. and 90% RH usually of
0.5 g/(m.sup.224 h) or less, preferably 0.4 g/(m.sup.224 h) or
less, and more preferably 0.3 g/(m.sup.224 h) or less. If the
blister molded sheet has poor steam barrier properties, moisture
may mingle with a medication in the PTP and may cause the quality
of the medication to deteriorate when the blister molded sheet is
used as a PTP for packing the medication.
[0406] The blister molded article of the present invention has
excellent oil resistance.
[0407] The oil resistance of the blister molded article can be
evaluated by applying salad oil (manufactured by Nisshin Oillio
Group, Ltd.) to the convex side (projection side) of the blister
molded article and placing the blister molded article in an oven
heated at 40.degree. C., and measuring the period of time elapsed
before the outward appearance changes. That period of time is
usually four days, preferably five days, more preferably six days,
and particularly preferably eight days.
[0408] The blister molding sheet of the present invention has
excellent blister moldability. The blister moldability (recess of
the pocket portion) of the blister molding sheet of the present
invention may be evaluated by arbitrarily selecting ten sheets of
PTP (number of pockets: five lengthwise, two in the lateral
direction, ten pockets in total), visually inspecting cylindrical
areas of 100 PTPs to count the number of the cylindrical areas of
which the bottom is inwardly dented or of which the swelling is
defective. The number of such defective cylindrical areas is
usually not more than 10, preferably not more than 5, more
preferably 1 or 0, and particularly preferably 0.
[0409] If there is an unevenness in the pocket of a blister molded
article which is processed as a PTP, the bottom of the cylindrical
upper part of the pocket may inwardly dent or the cylindrical part
may inadequately expand. Blister moldability can be evaluated by
evaluating such a dent and inadequate expansion.
[0410] As specific examples of the blister molded article,
containers and blister packs for medical supplies such as a press
through package (PTP), a syringe, and the like; foods; precision
components such as electric and electronic parts, semiconductor
parts, printed circuit boards; solar energy power generation system
components; fuel cell components; alcohol-containing fuel system
components; and the like may be given.
[0411] As an example of the method for preparing the resin
composition, a method of melt-kneading the hydrogenated norbornene
ring-open polymer of the present invention together with an
Antioxidant And other optional additives using a twin-screw
kneader, for example, at 200 to 400.degree. C., and producing
pellets, granules, or powder from the kneaded product can be
given.
10) Blow-Molded Container
[0412] The blow-molded container has at least one resin layer of a
hydrogenated norbornene ring-open polymer obtained by hydrogenating
80% or more of carbon-carbon double bonds of a ring-open polymer
which is obtained by ring-opening polymerization of 2-norbornene or
a monomer mixture of 2-norbornene and a substituent-containing
norbornene monomer. The proportion of a repeating unit (A) derived
from the 2-norbornene with respect to all repeating units is 90 to
100 wt % and the proportion of a repeating unit (B) derived from
the substituent-containing norbornene monomer with respect to all
repeating units is 0 to 10 wt %. The hydrogenated norbornene
ring-open polymer has a melting point of 110 to 145.degree. C.
[0413] Specifically, the hydrogenated norbornene ring-open polymer
used as the blow-molded container of the present invention is the
same as the hydrogenated norbornene ring-open polymer of the
present invention described above, except that the weight average
molecular weight (Mw) determined by gel permeation chromatography
(GPC) or the molecular weight distribution (Mw/Mn) of the
hydrogenated norbornene ring-open polymer may not be particularly
limited, when such a polymer is obtained by hydrogenating 80% or
more of main-chain carbon-carbon double bonds of a ring-open
polymer which is obtained by ring-opening polymerization of
2-norbornene (hydrogenated 2-norbornene ring-open polymer). The
polymers mentioned above as preferable examples of the hydrogenated
norbornene ring-open polymer of the present invention are
preferable hydrogenated norbornene ring-open polymers used as the
blow-molded container of the present invention.
[0414] The monomer mixture used for producing the hydrogenated
norbornene ring-open polymer used for the blow-molded container of
the present invention comprises usually 90 to 100 wt %, preferably
95 to 99 wt %, and more preferably 97 to 99 wt % of 2-norbornene
and usually 0 to 10 wt %, preferably 1 to 5 wt %, and more
preferably 1 to 3 wt % of the substituent-containing norbornene
monomers.
[0415] The proportion of the repeating unit (A) derived from
2-norbornene with respect to all repeating units of the
hydrogenated norbornene ring-open polymer used for the blow-molded
container of the present invention is usually 90 to 100 wt %,
preferably 95 to 99 wt %, and more preferably 97 to 99 wt %, and
the proportion of the repeating unit (B) derived from the
substituent-containing norbornene monomer with respect to all
repeating units of the hydrogenated norbornene ring-open polymer is
0 to 10 wt %, preferably 1 to 5 wt %, and more preferably 1 to 3 wt
%.
[0416] Various additives may be added to the hydrogenated
norbornene ring-open polymer used for the blow-molded container of
the present invention according to the purpose of application.
Examples of the additives include antioxidants, rubber-like
polymers and other resins, UV absorbers, weather-resistant
stabilizers, antistatic agents, slipping agents, anticlouding
agents, dyes, pigments, coloring agents, natural oils, synthetic
oils, plasticizers, organic or inorganic fillers, antibacterial
agents, deodorants, and the like. As specific examples of the
additives used for the blow-molded container of the present
invention, the same additives as those used for the multilayer
laminate of the present invention can be given. As specific
examples of the additives preferably used for the blow-molded
container of the present invention, the same additives as those
preferably used for the multilayer laminate of the present
invention can be given.
[0417] The blow-molded container of the present invention is a
monolayer or multilayer container obtained by blow molding the
hydrogenated norbornene ring-open polymer alone or together with
other thermoplastic resins.
[0418] As the method of blow molding, a method commonly used for
blow molding of thermoplastic resins such as direct blow molding,
injection blow molding, stretch blow molding, and multilayer blow
molding may be used. Among these methods, monolayer or multilayer
stretch blow molding is preferable. The method of blow molding will
now be described mainly taking the stretch blow molding as an
example.
[0419] In the stretch blow molding, a preform with a bottom is
first prepared by injecting the hydrogenated norbornene ring-open
polymer or a mixture of the hydrogenated norbornene ring-open
polymer and the other thermoplastic resin. Then, after adjusting
the temperature, the preform is molded by biaxial stretching blow
molding to obtaine a monolayer or multilayer blow-molded
article.
[0420] The cylinder temperature during molding the preform is
preferably 120 to 350.degree. C., more preferably 150 to
300.degree. C., and particularly preferably 160 to 250.degree. C.
The cylinder temperature in this range ensures appropriate melt
flowability of the resin while suppressing thermal decomposition to
obtain a blow-molded container with minimal distortion.
[0421] The pressure during perform molding is usually from 0.5 to
100 MPa, and preferably from 1 to 50 MPa. The pressure is applied
usually for about several seconds to several tens of minutes.
[0422] The preform molded by an injection mold is parted from the
injection mold at an injection mold temperature preferably from
(Tm-150.degree. C.) to (Tm-10.degree. C.), wherein Tm is a melting
point. The injection mold temperature in this range is preferable
from the viewpoint of preform shape stability.
[0423] When a heating instrument such as a heating pot is used for
controlling the preform temperature, the temperature of the heating
instrument is set preferably from 80 to 400.degree. C., more
preferably from 100 to 300.degree. C., and particularly preferably
from 120 to 200.degree. C. If the set temperature is too low, the
heating instrument cannot sufficiently function when the preform is
heated again; if the temperature is too high, the surface of the
preform and the blow-molded container may be yellowed or produce
burnt foreign matter.
[0424] Although there are no particular limitations, the distance
between the heating instrument and preform is preferably 1 to 50
mm, more preferably 2 to 25 mm, and particularly preferably 3 to 10
mm. If the distance between the heating instrument and preform is
in this range, the risk for the heating instrument to come in
contact with the preform is minimized and the preform can be
homogeneously heated.
[0425] The blow mold die temperature is appropriately selected
according to the type of the hydrogenated ring-open polymer
preferably from a range of (Tm-150.degree. C.) to (Tm-10.degree.
C.), and more preferably (Tm-130.degree. C.) to (Tm-10.degree. C.),
wherein Tm is the melting point of the hydrogenated ring-open
polymer. If the blow mold die temperature is in this range, the
residual stress decreases and the dimension of the container is
stabilized during storing for a long time. The blow pressure of
pressurized air or pressurized nitrogen used per one preform is
usually 0.1 to 5 MPa, preferably 0.3 to 3 MPa, and more preferably
0.5 to 1 MPa.
[0426] In the case of multilayer blow molding of the hydrogenated
norbornene ring-open polymer and another thermoplastic resin, these
blow molding conditions are suitably adjusted taking the blow
molding conditions of the other thermoplastic resin into
consideration.
[0427] In the process for manufacturing a multilayer preform,
molten resins are co-injected into a single preform die cavity
through one gate in one die clamping operation by a sequential
molding method or a simultaneous molding method using a molding
machine having a plural injection cylinders.
[0428] In the sequential molding method, injection timing of each
resin is adjusted to continuously and alternately inject resins so
that the multilayer preform may be produced by disposing the resin
injected earlier in inner/outer layers and disposing the resin
injected later in the middle layer. In the simultaneous molding
method, injection timing of each molten resin from the injection
cylinder is adjusted so that, at the initiation, a first resin is
injected first and a second resin is injected later. The two resins
are injected simultaneously and continuously to produce a
multilayer preform with the first resin in the inner/outer layers
and the second resin in the middle layer.
[0429] The blow molded container of the present invention is
preferably a stretch blow molded-container. In the stretch blow
molding process, after adjusting to a stretchable temperature, the
monolayer or multilayer preform is inserted into a blow molding die
cavity, and a pressurized fluid such as air is blown into the
cavity to carry out blow molding.
[0430] The stretch blow molding may be carried out by either a hot
parison system or a cold parison system.
[0431] A stretch magnification y in the vertical direction in the
stretch blow molding refers to a ratio of the length below the neck
of a blow-molded container (stretched part) to the length of the
preform below the neck (unstretched part), and a stretch
magnification x in the horizontal direction refers to the ratio of
the maximum diameter of the container in the horizontal direction
to the maximum diameter of the preform in the horizontal direction.
The maximum diameter refers to the greatest diameter when the
section of the preform and the blow-molded container are circular
and to the greatest equivalent diameter when the section is a
polygon or an ellipse form.
[0432] The stretch magnification y in the vertical direction is
preferably 1.1 to 25, more preferably 1.2 to 15, still more
preferably 1.5 to 10, and particularly preferably 1.8 to 8. The
stretch magnification x in the horizontal direction is preferably
1.1 to 25, more preferably 1.2 to 15, still more preferably 1.5 to
10, and particularly preferably 1.7 to 5. When the stretch
magnification y in the vertical direction and the stretch
magnification x in the horizontal direction are within these
ranges, a stretched blow molded article having excellent
transparency and producing cracks only with difficulty in the drop
test can be obtained.
[0433] The thickness of the blow-molded container is usually 0.1 to
30 mm, preferably 0.3 to 15 mm, and more preferably 0.5 to 10 mm.
The blow-molded container has a size of usually 10 to 2000 mm, and
preferably 50 to 2000 mm in all of the width, depth, and length. A
product obtained by sheet blow molding has a flat shape with a
width of usually 10 to 2000 mm, and preferably 50 to 1000 mm and a
depth of usually 0.1 to 100 mm, and preferably 0.5 to 50 mm.
[0434] The content of the hydrogenated norbornene ring-open polymer
in the layer which contains the hydrogenated norbornene ring-open
polymer in the blow-molded container of the present invention is
usually 50 to 100 wt %, preferably 70 to 100 wt %, and more
preferably 90 to 100 wt %. This thickness range is preferable
because the characteristics possessed by the hydrogenated
norbornene ring-open polymer such as steam barrier properties are
not affected.
[0435] The thickness of the hydrogenated norbornene ring-open
polymer in the layer which contains the hydrogenated norbornene
ring-open polymer in the blow-molded container of the present
invention is usually 0.005 to 30 mm, preferably 0.01 to 10 mm, and
more preferably 0.05 to 5 mm. This thickness range is preferable
because the characteristics possessed by the layer containing the
hydrogenated norbornene ring-open polymer such as steam barrier
properties are not affected.
[0436] The blow-molded container may have a shape of a cylinder, a
square pillar, a globe, and the like. The cylinder and square
pillar are preferable from the viewpoint of impact strength and the
like. The blow-molded container may also have a skirt-like shape
spreading from the opening toward the bottom, a shape with a
swelling in the central part in the height direction, or the like.
There are no particular limitations to the bottom shape of the
blow-molded article. The blow-molded article may have a flat shape
or a shape with a depressed portion toward the inside.
[0437] The blow-molded container of the present invention may be
provided with a painted pattern design, a printed ornament, and the
like on the surface or a part thereof A surface treatment may be
applied to the blow-molded container in order to increase
adhesiveness of a printing layer to the blow-molded container. As
specific examples of the surface treatment, a corona discharge
treatment, a plasma treatment, a flame treatment, a resin
application, and a hot stamp can be given.
[0438] The blow-molded container may be annealed in order to
accelerate crystallization.
[0439] Since the hydrogenated norbornene ring-open polymer of the
present invention is a crystalline polymer having a melting point,
if crystal areas are formed in the polymer forming the blow-molded
container, the crystal areas provide the molded container with good
mechanical properties in combination with amorphous areas, and yet
the polymer maintains excellent transparency due to a small degree
of crystallinity.
[0440] The blow-molded container of the present invention may be a
multilayer blow-molded container having a layer of the hydrogenated
norbornene ring-open polymer and another thermoplastic resin layer.
Any resin material commonly used for food and medical application
may be used as the resin forming the layer of the other
thermoplastic resin without particular limitations.
[0441] As examples of the thermoplastic resin, various synthetic
resins, for example, polyolefin resins such as polyethylene and
polypropylene; thermoplastic polyester resins such as polyethylene
terephthalate and polybuthylene terephthalate; gas barrier resins
such as polyvinylidene chloride, ethylene-vinyl alcohol copolymer
(EVOH), polyvinyl alcohol, and polyamide; polymethyl methacrylate,
polycarbonate, ionomer resin, polystyrene, ABS resin, thermoplastic
elastomer, ethylene-vinyl acetate copolymer, and polysulfone can be
given.
[0442] As examples of the polyolefin resin, polyolefin crystalline
resins in the group consisting of polyethylene resins such as a
linear or branched high density polyethylene, low density
polyethylene, and ultra-high polymer polyethylene; polypropylene
resins such as linear or branched high density polypropyrene and
low density polypropyrene; ethylene-propylene copolymer,
polymethylpentene, polybutene, polymethylbutene, and
polymethylhexene; and the like can be given.
[0443] The blow-molded container of a multilayer laminate is
preferable due to increased pliability, impact resistance, heat
resistance, and gas barrier properties. Use of a gas barrier resin
such as an ethylene-vinyl alcohol copolymer, nylon, or the like as
a material for another layer is particularly preferable because of
excellent gas barrier properties of the resulting blow-molded
container. Either one layer or two or more layers of the
hydrogenated norbornene ring-open polymer and the other
thermoplastic resin may be provided.
[0444] There are no particular limitations to the constitution of
the multilayer laminate inasmuch as such a multilayer laminate
contains a layer of the hydrogenated norbornene ring-open polymer
and a layer of the other thermoplastic resin. The following
constitutions can be given as specific examples. In the following
constitutions, the layer containing the hydrogenated ring-open
polymer is indicated as "NB layer" and the other resin layers are
indicated as "synthetic resin layer".
(1) NB layer/synthetic resin layer (2) NB layer/synthetic resin
layer/NB layer (3) Synthetic resin layer/NB layer/synthetic resin
layer (4) NB layer/synthetic resin layer/synthetic resin layer/NB
layer (5) NB layer/synthetic resin layer/NB layer/synthetic resin
layer (6) NB layer/synthetic resin layer/NB layer/synthetic resin
layer/NB layer (7) Synthetic resin layer/synthetic resin layer/NB
layer/synthetic resin layer/synthetic resin layer (8) Synthetic
resin layer/NB layer/synthetic resin layer/NB layer/synthetic resin
layer
[0445] The above layer constitutions are preferable examples but
the blow-molded container of the present invention is not limited
to these. An adhesive layer may optionally be provided between the
layers.
[0446] In addition, the blow-molded container of the present
invention may be provided with a metallic foil such as an aluminum
foil, an aluminum vapor deposition film, a laminate film of a
metallic foil and a synthetic resin film, a layer which has a light
blocking effect (shading layer) such as a synthetic resin film with
a pigment incorporated therein. Among these shading layers,
aluminum foil and an aluminum vapor deposition film, and the like
have not only shading properties, but also damp-proofing
properties, oil resistance, non-water-absorbing properties.
Therefore, these shading layers can provide a blow-molded container
with the capability of storing chemicals and the like for a long
period of time. When co-extrusion is impossible, these shading
layers may be added to the blow-molded container by lamination or
the like. As specific layer constitutions,
(1) NB layer/synthetic resin layer/shading layer, (2) NB
layer/synthetic resin layer/shading layer/synthetic resin layer,
(3) NB layer/shading layer, and the like can be given.
[0447] It is possible to employ other desired multilayer
constitutions according to the purpose of use, such as those having
a larger number of layers in addition to any one of the above layer
combinations.
[0448] Although not particularly limited, the multilayer blow
molded container is generally fabricated by multilayer coextrusion
blow molding or coinjection stretching blow molding. It is also
possible to multilayer a blow molded container after molding by a
method of attaching a resin film using an adhesive, a method of
bonding by fusing the resin film by heating or high frequency to a
temperature above the melting point, a method of applying a resin
solution in an organic solvent and drying the coating, and the
like.
[0449] The blow molded container of the present invention has
excellent steam barrier properties, heat resistance, transparency,
and oil resistance, as well as high mechanical strength. The blow
molded container of the present invention has an advantage of a
wide processing temperature range due to the high thermal
decomposition temperature of the hydrogenated norbornene ring-open
polymer.
[0450] The blow molded container of the present invention has
excellent steam barrier properties. It is possible to reduce the
moisture permeability (g/(m.sup.224 h)) per 1 mm thickness of the
barrel (side) of the blow molded container of the present invention
measured based on JIS K7129 to usually 0.045 g/(m.sup.224 h) or
less, preferably 0.035 g/(m.sup.224 h) or less, and more preferably
0.03 g/(m.sup.224 h) or less.
[0451] The blow molded container of the present invention has
excellent oil resistance. The surface of the blow molded container
of the present invention with a thickness of 1 mm is not whitened
after immersing in an n-heptane test solution for 10 minutes.
[0452] The blow molded container of the present invention has
excellent transparency. The blow molded container of the present
invention with a thickness of 1 mm has a haze of usually 40% or
less, preferably 30% or less, and more preferably 20% or less.
[0453] The blow molded container of the present invention which has
these characteristics can be used for a wide variety of
applications in the fields of food industries, medical supplies,
cosmetics, energy, optical appliances, electric and electronic
parts, telecommunications sector, vehicles, public welfare, toys,
instruments for physics and chemistry, civil engineering and
construction, and the like. Among these fields, the blow molded
container of the present invention is particularly suitable in the
fields of food industries, medical supplies, cosmetics, and
energy.
EXAMPLES
[0454] The present invention will be described below more
specifically by way of Examples and Comparative Examples, which are
not intended to limit the present invention. In the Examples and
Comparative Examples, "part(s)" means "part(s) by weight" and "%"
means "wt %" unless otherwise indicated.
[0455] In the following Examples and Comparative Examples, various
properties were measured by the following methods.
(A) Polymer Properties
[0456] (1) The weight average molecular weight (Mw) and the number
average molecular weight (Mn) of the ring-open polymers were
measured as standard polystyrene-reduced values by gel permeation
chromatography (GPC) using toluene as an eluant.
[0457] As the measuring device, GPC-8020 series instruments
(DP8020, SD8022, AS8020, CO8020, and RI8020 manufactured by Tosoh
Corp.) were used.
[0458] As the standard polystyrene, standard polystyrene having an
Mw of a total of eight points, 500, 2630, 10,200, 37,900, 96,400,
427,000, 1,090,000, and 5,480,000, (manufactured by, Tosoh Corp.)
was used.
[0459] The sample was prepared by dissolving the polymer to be
analyzed in toluene to a concentration of 1 mg/ml and filtering
through a cartridge filter (made of polytetrafluoroethylene, pore
size: 0.5 .mu.m).
[0460] The molecular weight was measured by feeding a sample to two
TSKgeI GMHHR-H columns (manufactured by Tosoh Corp.) connected in
series at a flow rate of 1.0 ml/min in an amount of 100 .mu.ml at a
column temperature of 40.degree. C.
(2) The weight average molecular weight (Mw) and the number average
molecular weight (Mn) of the hydrogenated ring-open polymers were
measured as standard polystyrene-reduced values by gel permeation
chromatography (GPC) using 1,2,4-trichlorobenzene as an eluant.
[0461] HLC8121GPC/HT (manufactured by Tosoh Corp.) was used as a
measuring device.
[0462] As the standard polystyrene, standard polystyrene having an
Mw of a total of 16 points, 988, 2580, 5910, 9010, 18,000, 37,700,
95,900, 18,6000, 351,000, 889,000, 1,050,000, 2,770,000, 5,110,000,
7,790,000, and 20,000,000 (manufactured by, Tosoh Corp.) was
used.
[0463] The sample was prepared by dissolving the polymer to be
analyzed in 1,2,4-trichlorobenzene with heating at 140.degree. C.
to a concentration of 1 mg/ml.
[0464] The molecular weight was measured by feeding a sample to
three TSKgel GMHHR-H (20)HT columns (manufactured by Tosoh Corp.)
connected in series at a flow rate of 1.0 ml/min in an amount of
300 .mu.ml at a column temperature of 140.degree. C.
(3) The degree of hydrogenation of the hydrogenated ring-open
polymer was determined by .sup.1H-NMR spectrum measurement using
deuteriochloroform as a solvent. (4) The isomerization ratio was
calculated using an equation, [33.0 ppm peak integration
value]/([31.8 ppm peak integration value]+[33.0 ppm peak
integration value]).times.100, wherein the peak integration value
was determined by .sup.13C-NMR spectrum measurement using
deuteriochloroform as a solvent.
[0465] The 31.8 ppm peak is a peak derived from cis-isomers of
2-norbornene repeating units in the polymer and the 33.0 ppm peak
is a peak derived from trans-isomers of 2-norbornene repeating
units in the polymer.
(5) Melting point was measured according to JIS K7121 using a
differential scanning calorimeter (DSC6220SII manufactured by
NanoTechnology Inc.) after heating the sample to a temperature
30.degree. C. higher than the melting point, cooling the sample to
room temperature at a cooling rate of -10.degree. C./min, and
heating at a rate of 10.degree. C./min. (6) Glass transition
temperature was measured according to JIS K6911 using a
differential scanning calorimeter (DSC6220SII manufactured by
NanoTechnology Inc.).
(B) Tube Sheet Properties
[0466] (1) Thickness of the sheet was measured using a micro gage.
(2) Uneven thickness of the sheet was measured by applying five
marks on the film at 4 cm intervals in the direction (TD direction)
vertical to the flow direction of the sheet, applying 20 marks at
20 cm intervals in the flow direction (MD direction) of the sheet
starting from the first five marks, thereby applying 100 marks in
total, measuring the film thickness at 100 marked points, and
calculating the standard deviation from the results. The smaller
the value of the standard deviation, the smaller the thickness
unevenness of the sheet. (3) The steam barrier properties of the
sheet was measured according to JIS K7129 (method A) using a
moisture permeability tester (L80-5000 type, manufactured by LYSSY)
under conditions of a temperature of 50.degree. C. and humidity of
90% RH. A small moisture permeability (g/(m.sup.224 h)) indicates
good steam barrier properties. (4) Modulus of elasticity of the
sheet was measured according to ISO 527 using a 1B shape test
specimen obtained from the sheet at a tensile velocity of 200
mm/min using Autograph (AGS-5kNH, manufactured by Shimadzu Corp.).
The test specimen was prepared so that its longitudinal direction
is the TD direction of the tube sheet. (5) Mechanical properties of
the sheet were measured by inspecting a strain on the surface at
the time of cracks according to ISO 527 using a 1B shape test
specimen prepared from the sheet at a tensile velocity of 200
mm/min using Autograph (AGS-5kNH, manufactured by Shimadzu Corp.).
The test specimen was prepared so that its longitudinal direction
is the TD direction of the tube sheet. (6) Oil resistance of the
sheet was evaluated by measuring the haze value before and after
dipping a film prepared from the tube sheet in salad oil for one
hour according to JIS-K7136 using a haze meter (NDH 200A
manufactured by Nihon Denshoku Industries Co., Ltd.), and dividing
the haze value of the untreated sheet with the haze value after
treatment. The smaller the value, the worse the haze and the poorer
the oil resistance.
(C) Properties of Blister-Molded Article
[0467] (1) Thickness of the film was measured using a micro gage.
(2) The steam barrier properties was evaluated by measuring the
moisture permeability according to JIS K7129 (method A) using a
moisture permeability tester (L80-5000 type, manufactured by LYSSY)
under conditions of a temperature of 40.degree. C. and humidity of
90% RH and conditions of a temperature of 50.degree. C. and
humidity of 90% RH. A small moisture permeability (g/(m.sup.224 h))
indicates good steam barrier properties. (3) The oil resistance was
evaluated by applying salad oil (manufactured by Nisshin Oillio
Group, Ltd.) to the convex side (projected side) of the
blister-molded articles, placing the sample in an oven heated at
40.degree. C., and measuring the period of time elapsed before the
outward appearance of the sample changes. The longer the time
elapsed before the outward appearance of the blister-molded article
changes, the better the oil resistance. (4) The blister moldability
was evaluated by arbitrarily selecting ten sheets of PTP (number of
pockets: five lengthwise, two in the lateral direction, total ten
pockets), visually inspecting cylindrical areas of 100 PTPs to
count the number of cylindrical areas of which the bottom is
inwardly dented or the number of cylindrical areas of which the
swelling is defective. The smaller the number of the PTPs having
cylindrical areas of which the swelling is defective, the better
the blister moldability.
[0468] If there is an uneven thickness in the pocket of a blister
molded article which is processed as a PTP, the bottom of the
cylindrical upper part of the pocket may inwardly dent or the
cylindrical part may inadequately expand. Blister moldability can
be evaluated by evaluating such a dent and inadequate
expansion.
(D) Properties of Multilayer Laminate
[0469] (1) Thickness of the film was measured using a micro gage.
(2) The impact resistance was evaluated by preparing bags (n=100)
with a size of 20 cm.times.20 cm, sealing the four sides of the
bags with heat, putting brine in the bags, and dropping the bags
from a height of 3 m, observing the presence or absence of cracks
after dropping, and counting the number of cracked bags. The
smaller the number of cracks, the better the impact resistance. (3)
The steam barrier properties were evaluated by measuring moisture
permeability according to JIS K7129 (method A) using a moisture
permeability tester (L80-5000 type, manufactured by LYSSY) under
conditions of a temperature of 50.degree. C. and humidity of 90%
RH. A small moisture permeability (g(m.sup.224 h)) indicates good
steam barrier properties. (4) The oil resistance was evaluated by
cutting a 5 cm square from the film, dipping the sample in salad
oil (manufactured by Nisshin Oillio Group, Ltd.) for 30 seconds,
and placing the sample in an oven heated at 40.degree. C., and
measuring the period of time elapsed before the outward appearance
of the sample changes. The longer the time elapsed before the
outward appearance of the film changes, the better the oil
resistance. (5) The gas barrier properties were evaluated by
boiling the film in boiling water for 30 minutes and measuring the
gas barrier properties before and after boiling according to MS
K7126 (method B) under conditions of a temperature of 23.degree. C.
and humidity of 0% RH using an oxygen permeability tester (OPT-5000
type, manufactured by LYSSY). A small oxygen permeability
(cm.sup.3m.sup.-2day.sup.-1atm.sup.-1 indicates ndicates good steam
barrier properties.
(E) Properties of Blow-Molded Container
[0470] (1) Blow moldability was evaluated by measuring the
thickness t of the body of the blow-molded container by applying a
probe of an ultrasonic thickness meter (manufactured by KARL
DEUTSCH) to the side of the blow-molded container body.
Specifically, the blow-molded container was placed on a horizontal
plane and the thickness was measured at 100 points starting from a
point 10 mm from the horizontal plane at 5 mm intervals. The
standard deviation (.sigma.) was calculated. (2) The steam barrier
properties were evaluated by measuring moisture permeability
according to JIS K7129 (method A) using a moisture permeability
tester (L80-5000 type, manufactured by LYSSY) under conditions of a
temperature of 40.degree. C. and humidity of 90% RH. A small
moisture permeability (g/(m.sup.224 h)) indicates good steam
barrier properties. The test for steam barrier properties was
carried out using a plate-like sample prepared from the blow-molded
container. (3) A falling-weight impact resistance was evaluated by
filling the blow-molded containers with brine in an amount
equivalent to 90% of the total volume, dropping the container from
a height (from the ground to the bottom of the container) of 1 m,
and observing the conditions of the containers after falling. The
number of containers with no cracks or leaks among 30 tested
containers was counted. (4) The normal heptane impregnation test
was carried out as an oil resistance evaluation test. 2.5 l of
n-heptane (manufactured by Wako Pure Chemical Industries, Ltd.) was
added to a 3 l glass beaker. The sample containers were immersed in
n-heptane in the glass beaker. The condition of the sample
container surface (whether the surface was whitened or not and
cracked or not) was observed after 10 minutes of immersion. (5)
Haze (%) was measured by preparing samples with a thickness of 1 mm
by cutting the blow-molded container and measuring the samples
using a haze meter ("NDH2000" manufactured by Nippon Denshoku Co.,
Ltd.).
(F) Properties of Molding Material
[0471] (1) The amount of organic substances discharged was measured
by washing 5 g of the molding material sample with a large amount
of ultra pure water in a clean room (class 1000), placing the
sample in a glass sample container completely free from moisture
and organic substances adhering to the surface, heating the sample
container at 80.degree. C. for 60 minutes, and measuring gases
discharged from the sample container by heat desorption gas
chromatography mass spectrometer (TDS-GC-MS manufactured by Agilent
Technologies). (2) The heat resistance of the container was
confirmed by allowing a wafer carrier produced from the molding
material to stand at a temperature of 105.degree. C. for 30 minutes
and observing whether or not the wafer carrier was deformed. The
sample was rated as "Good" if the wafer was not deformed and as
"Bad" if the wafer was deformed. (3) The content of transition
metals was measured using an inductively coupled plasma optical
emission spectrometry (IRIS Advantage/SSEA, manufactured by Nippon
Jarrell-Ash Co. Ltd.). (4) In measuring an increased amount of
foreign matter, a new 8-inch bear silicon wafer purchased packed in
a polypropylene wafer shipper was immersed in a 4.5 wt % solution
of hydrofluoric acid at 25.degree. C. for one minute to remove a
thin silicon oxide film in a clean room (class 1000), and then
immersed in a 50:1 (by vol) mixture of 98% concentrated sulfuric
acid and a 30% hydrogen peroxide aqueous solution at 110.degree. C.
for 10 minutes. Next, after removing organic substances by
immersing in concentrated sulfuric acid at 65.degree. C. for 10
minutes and washing away the acid with a large amount of ultra-pure
water and completely removing water by a centrifugal separator, the
number of foreign matter particles on the dried wafer was counted
using a foreign matter detector (Surfscan SP1 manufactured by
KLA-Tencor corp.). After the wafer was inserted in and removed from
the molded wafer carrier 50 times, the number of foreign matter
particles on the wafer was counted again. The increased amount of
foreign matter was evaluated by the difference of the number of
foreign matter particles before and after the test.
Example 1
Ring-Opening Polymerization
[0472] A reactor was charged with 500 parts by weight of dehydrated
cyclohexane, 0.55 parts by weight of 1-hexene, 0.30 parts by weight
of diisopropyl ether, 0.20 parts by weight of triisobutylaluminum,
and 0.075 parts by weight of isobutyl alcohol at room temperature
under a nitrogen atmosphere. While maintaining the temperature at
55.degree. C., 250 parts by weight of 2-norbornene and 15 parts by
weight a 1.0 wt % solution of tungsten hexachloride in toluene were
continuously added in two hours to polymerize the monomers. The
weight average molecular weight (Mw) of the resulting ring-open
polymer (1) was 83,000, and the molecular weight distribution
(Mw/Mn) was 1.8.
(Hydrogenation Reaction)
[0473] The polymerization reaction solution containing the
ring-open polymer (1) obtained above was transferred to a pressure
resistant hydrogenation reactor. After the addition of 0.5 parts by
weight of a nickel catalyst supported by diatomaceous earth (T8400,
nickel support rate: 58 wt %, manufactured by Nissan-Sud-Chemie),
the hydrogenation reaction was carried out at 160.degree. C. under
a hydrogen pressure of 4.5 MPa for six hours. The reaction solution
was filtered through a stainless steel wire mesh filter, in which
diatomaceous earth was used as a filtration adjuvant, to remove the
catalyst.
[0474] The filtrate was poured into 3000 parts by weight of
isopropyl alcohol while stirring to precipitate the hydrogenated
product. After washing with 500 parts by weight of acetone, the
hydrogenated product was dried in a vacuum dryer at 100.degree. C.
under 0.13.times.10.sup.3 Pa for 48 hours to obtain 190 parts by
weight of a hydrogenated ring-open polymer (1).
(Properties of Polymer)
[0475] The degree of hydrogenation of the resulting hydrogenated
ring-open polymer (1) was 99.9%, the weight average molecular
weight (Mw) was 82,200, the molecular weight distribution (Mw/Mn)
was 2.9, the isomerization ratio was 5%, and the melting point was
140.degree. C.
(Preparation of Resin Composition)
[0476] 0.1 part by weight of
tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methan-
e (Irganox 1010 manufactured by Ciba Geigy, hereinafter referred to
as "Antioxidant A") was added to 100 parts by weight of a
hydrogenated ring-open polymer (1) and the mixture was kneaded
using a twin-screw kneader (TEM35 manufactured by Toshiba Machine
Co., Ltd.) to obtain pellets.
(Preparation of Resin Sheet)
[0477] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
150.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (1).
Example 2
Hydrogenation Reaction
[0478] A polymerization reaction solution containing the ring-open
polymer (1) obtained in the same manner as in Example 1 was
transferred to a pressure resistant hydrogenation reactor. After
the addition of 1.0 part by weight of a nickel catalyst supported
by diatomaceous earth (T8400, nickel support rate: 58 wt %,
manufactured by Nissan-Sud-Chemie), the hydrogenation reaction was
carried out at 165.degree. C. under a hydrogen pressure of 4.5 MPa
for six hours. The reaction solution was filtered through a
stainless steel wire mesh filter, in which diatomaceous earth was
used as a filtration adjuvant, to remove the catalyst. The filtrate
was poured into 3000 parts by weight of isopropyl alcohol while
stirring to precipitate the hydrogenated product. After washing
with 500 parts by weight of acetone, the hydrogenated product was
dried in a vacuum dryer at 100.degree. C. under 0.13.times.10.sup.3
Pa for 48 hours to obtain 190 parts by weight of a hydrogenated
ring-open polymer (2).
(Properties of Polymer)
[0479] The degree of hydrogenation of the resulting hydrogenated
ring-open polymer (2) was 99.9%, the weight average molecular
weight (Mw) was 82,000, the molecular weight distribution (Mw/Mn)
was 2.8, the isomerization ratio was 15%, and the melting point was
134.degree. C.
(Preparation of Resin Composition)
[0480] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (2) and the mixture
was kneaded using a twin-screw kneader (TEM35 manufactured by
Toshiba Machine Co., Ltd.) to obtain a pelletized resin
composition.
(Preparation of Resin Sheet)
[0481] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
145.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (2).
Example 3
Hydrogenation Reaction
[0482] A polymerization reaction solution containing the ring-open
polymer (1) obtained in the same manner as in Example 1 was
transferred to a pressure resistant hydrogenation reactor. After
the addition of 4 parts by weight of a nickel catalyst supported by
diatomaceous earth (T8400, nickel support rate: 58 wt %,
manufactured by Nissan-Sud-Chemie), the hydrogenation reaction was
carried out at 180.degree. C. under a hydrogen pressure of 4.5 MPa
for six hours. The reaction solution was filtered through a
stainless steel wire mesh filter, in which diatomaceous earth was
used as a filtration adjuvant, to remove the catalyst. The filtrate
was poured into 3000 parts by weight of isopropyl alcohol while
stirring to precipitate the hydrogenated product.
[0483] After washing with 500 parts by weight of acetone, the
hydrogenated product was dried in a vacuum dryer at 100.degree. C.
under 0.13.times.10.sup.3 Pa for 48 hours to obtain 190 parts by
weight of a hydrogenated ring-open polymer (3).
(Properties of Polymer)
[0484] The degree of hydrogenation of the resulting ring-open
polymer (3) was 99.9%, the weight average molecular weight (Mw) was
81,600, the molecular weight distribution (Mw/Mn) was 2.8, the
isomerization ratio was 35%, and the melting point was 125.degree.
C.
(Preparation of Resin Composition)
[0485] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (3) and the mixture
was kneaded using a twin-screw kneader (TEM35 manufactured by
Toshiba Machine Co., Ltd.) to obtain a pelletized resin
composition.
(Preparation of Resin Sheet)
[0486] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
135.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (3).
Example 4
Ring-Opening Polymerization
[0487] A polymerization reaction was carried out in the same manner
as in Example 1 except for using 0.20 parts by weight of 1-hexene,
0.40 parts by weight of diisopropyl ether, 0.27 parts by weight of
triisobutylaluminum, 0.10 part by weight of isobutyl alcohol, and
20 parts by weight of a 1.0% tungsten hexachloride solution in
toluene, to obtain a reaction solution containing a ring-open
polymer (2). The weight average molecular weight (Mw) of the
resulting ring-open polymer (2) was 153,000, and the molecular
weight distribution (Mw/Mn) was 3.0.
(Hydrogenation Reaction)
[0488] The reaction solution containing the ring-open polymer (2)
obtained above was transferred to a pressure resistant
hydrogenation reactor. After the addition of 2 parts by weight of a
nickel catalyst supported by diatomaceous earth (T8400, nickel
support rate: 58 wt %, manufactured by Nissan-Sud-Chemie), the
hydrogenation reaction was carried out at 160.degree. C. under a
hydrogen pressure of 4.5 MPa for six hours. The reaction solution
was filtered through a stainless steel wire mesh filter, in which
diatomaceous earth was used as a filtration adjuvant, to remove the
catalyst. The filtrate was poured into 3000 parts by weight of
isopropyl alcohol while stirring to precipitate the hydrogenated
product. After washing with 500 parts by weight of acetone, the
hydrogenated product was dried in a vacuum dryer at 100.degree. C.
under 0.13.times.10.sup.3 Pa for 48 hours to obtain 190 parts by
weight of a hydrogenated ring-open polymer (4).
(Properties of Polymer)
[0489] The degree of hydrogenation of the resulting hydrogenated
ring-open polymer (4) was 99.9%, the weight average molecular
weight (Mw) was 150,500, the molecular weight distribution (Mw/Mn)
was 4.0, the isomerization ratio was 9%, and the melting point was
136.degree. C.
(Preparation of Resin Composition)
[0490] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (4) and the mixture
was kneaded using a twin-screw kneader (TEM35 manufactured by
Toshiba Machine Co., Ltd.) to obtain a pelletized resin
composition.
(Preparation of Resin Sheet)
[0491] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
150.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (4).
Example 5
Ring-Opening Polymerization
[0492] A solution containing a ring-open polymer (3) was obtained
in the same manner as in Example 1 except for using 0.10 part by
weight of 1-hexene, 0.40 parts by weight of diisopropyl ether, 0.27
parts by weight of triisobutylaluminum, 0.10 part by weight of
isobutyl alcohol, and 20 parts by weight of a 1.0% tungsten
hexachloride solution in toluene.
[0493] The weight average molecular weight (Mw) of the resulting
ring-open polymer (3) was 189,500, and the molecular weight
distribution (Mw/Mn) was 3.3.
(Hydrogenation Reaction)
[0494] The reaction solution containing the ring-open polymer (3)
obtained above was transferred to a pressure resistant
hydrogenation reactor. After the addition of 1 part by weight of a
nickel catalyst supported by diatomaceous earth (T8400, nickel
support rate: 58 wt %, manufactured by Nissan-Sud-Chemie), the
hydrogenation reaction was carried out at 160.degree. C. under a
hydrogen pressure of 4.5 MPa for six hours. The reaction solution
was filtered through a stainless steel wire mesh filter, in which
diatomaceous earth was used as a filtration adjuvant, to remove the
catalyst. The filtrate was poured into 3000 parts by weight of
isopropyl alcohol while stirring to precipitate the hydrogenated
product. After washing with 500 parts by weight of acetone, the
hydrogenated product was dried in a vacuum dryer at 100.degree. C.
under 0.13.times.10.sup.3 Pa for 48 hours to obtain 190 parts by
weight of a hydrogenated ring-open polymer (5).
(Properties of Polymer)
[0495] The degree of hydrogenation of the resulting hydrogenated
ring-open polymer (5) was 99.9%, the weight average molecular
weight (Mw) was 185,000, the molecular weight distribution (Mw/Mn)
was 4.4, the isomerization ratio was 10%, and the melting point was
136.degree. C.
(Preparation of Resin Composition)
[0496] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (5) and the mixture
was kneaded using a twin-screw kneader (TEM35 manufactured by
Toshiba Machine Co., Ltd.) to obtain a pelletized resin
composition.
(Preparation of Resin Sheet)
[0497] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
150.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (5).
Comparative Example 1
Ring-Opening Polymerization
[0498] A reaction solution containing a norbornene ring-open
polymer (4) was obtained in the same manner as in Example 1, except
for using 1.3 parts by weight of 1-hexene. The weight average
molecular weight (Mw) of the resulting ring-open polymer (4) was
39,800, and the molecular weight distribution (Mw/Mn) was 1.7.
(Hydrogenation Reaction)
[0499] The reaction solution containing the ring-open polymer (4)
obtained above was transferred to a pressure resistant
hydrogenation reactor. After the addition of 0.5 parts by weight of
a nickel catalyst supported by diatomaceous earth (T8400, nickel
support rate: 58 wt %, manufactured by Nissan-Sud-Chemie), the
hydrogenation reaction was carried out at 160.degree. C. under a
hydrogen pressure of 4.5 MPa for six hours. The solution was
filtered through a stainless steel wire mesh filter, in which
diatomaceous earth was used as a filtration adjuvant, to remove the
catalyst. The filtrate was poured into 3000 parts by weight of
isopropyl alcohol while stirring to precipitate the hydrogenated
product. After washing with 500 parts by weight of acetone, the
hydrogenated product was dried in a vacuum dryer at 100.degree. C.
under 0.13.times.10.sup.3 Pa for 48 hours to obtain 190 parts by
weight of a hydrogenated ring-open polymer (6).
(Properties of Polymer)
[0500] The degree of hydrogenation of the resulting hydrogenated
ring-open polymer (6) was 99.9%, the weight average molecular
weight (Mw) was 38,200, the molecular weight distribution (Mw/Mn)
was 2.6, the isomerization ratio was 6%, and the melting point was
142.degree. C.
(Preparation of Resin Composition)
[0501] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (6) and the mixture
was kneaded using a twin-screw kneader (TEM35 manufactured by
Toshiba Machine Co., Ltd.) to obtain a pelletized resin
composition.
(Preparation of Resin Sheet)
[0502] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
150.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (6).
Comparative Example 2
Ring-Opening Polymerization
[0503] An autoclave equipped with a stirrer was charged with 1.1
parts by weight of tungsten (phenylimide) tetrachloride diethyl
ether and 18.5 parts by weight of cyclohexane. A solution of 0.87
parts by weight of diethylaluminum ethoxide in 9.26 parts by weight
of hexane was further added and the mixture was stirred for 30
minutes at room temperature. After the addition of 139 parts by
weight of dicyclopentadiene and 0.33 parts by weight of 1-hexene,
the polymerization reaction was carried out at 50.degree. C. for
three hours to obtain a reaction solution containing a ring-open
polymer (5).
[0504] The weight average molecular weight (Mw) of the resulting
ring-open polymer (5) was 78,000, and the molecular weight
distribution (Mw/Mn) was 3.5.
(Hydrogenation Reaction)
[0505] A hydrogenation catalyst solution containing 0.87 parts by
weight of bis(tricyclohexylphosphine)benzylidyne ruthenium (IV)
dichloride and 20.4 parts by weight of ethyl vinyl ether dissolved
in 650 parts by weight of cyclohexane was added to the resulting
polymer solution, and the hydrogenation reaction was carried out at
160.degree. C. under a hydrogen pressure of 1.0 MPa for 20 hours.
The reaction solution was poured into a large amount of isopropanol
to cause the polymer to completely precipitate. The precipitate was
collected by filtration. After washing with 500 parts by weight of
acetone, the precipitate was dried in a vacuum dryer at 100.degree.
C. under 0.13.times.10.sup.3 Pa for 48 hours to obtain 130 parts by
weight of a hydrogenated ring-open polymer (7).
[0506] Since the hydrogenated ring-open polymer (7) was insoluble
in the GPC solvent, the molecular weight could not be measured. The
melting point was 273.degree. C.
(Preparation of Resin Composition)
[0507] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (7) and the mixture
was kneaded using a twin-screw kneader (TEM35 manufactured by
Toshiba Machine Co., Ltd.) to obtain a pelletized resin
composition.
(Preparation of Resin Sheet)
[0508] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
280.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (7).
Reference Example 1
Ring-Opening Polymerization
[0509] An autoclave equipped with a stirrer was charged with 37.5
parts by weight of a 70 wt % norbornene solution in toluene, 0.052
parts by weight of 1-hexene, and 49.3 parts by weight of
cyclohexane, and the mixture was stirred. Then, a solution
containing 0.023 parts by weight of 2,6-diisopropylphenylimide
neophylidene molybdenum (VI) bis(t-butoxide) and 0.016 parts by
weight of trimethylphosphine in 8.6 parts by weight of toluene were
added, and the reaction was carried out at 30.degree. C. for one
hour. 0.40 parts by weight of benzaldehyde was added to the
reaction mixture to obtain a reaction solution containing a
ring-open polymer (6).
[0510] The weight average molecular weight (Mw) of the resulting
ring-open polymer (6) was 65,000, and the molecular weight
distribution (Mw/Mn) was 1.1.
(Hydrogenation Reaction)
[0511] The reaction solution containing the ring-open polymer (6)
obtained above was transferred to a pressure resistant
hydrogenation reactor. After the addition of 5.25 parts by weight
of Pd/CaCO.sub.3 (amount of Pd: 5 wt %, manufactured by Strem
Chemicals, Inc.) as a catalyst, the hydrogenation reaction was
carried out at 100.degree. C. under a hydrogen pressure of 3.5 MPa
for 48 hours. The reaction solution was filtered through a
stainless steel wire mesh filter, in which diatomaceous earth was
used as a filtration adjuvant, to remove the catalyst. The filtrate
was poured into 3000 parts by weight of isopropyl alcohol while
stirring to precipitate the hydrogenated product. After washing
with 500 parts by weight of acetone, the hydrogenated product was
dried in a vacuum dryer at 100.degree. C. under 0.13.times.10.sup.3
Pa for 48 hours to obtain 190 parts by weight of a hydrogenated
ring-open polymer (8).
(Properties of Polymer)
[0512] The degree of hydrogenation of the resulting hydrogenated
ring-open polymer (8) was 99.75%, the weight average molecular
weight (Mw) was 64,200, the molecular weight distribution (Mw/Mn)
was 1.3, the isomerization ratio was 0%, and the melting point was
143.degree. C.
(Preparation of Resin Composition)
[0513] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (8) and the mixture
was kneaded using a twin-screw kneader (TEM35 manufactured by
Toshiba Machine Co., Ltd.) to obtain a pelletized resin
composition.
(Preparation of Resin Sheet)
[0514] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
150.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (8).
Comparative Example 3
Ring-Opening Polymerization and Hydrogenation Reaction
[0515] Polymerization was carried out in the same manner as in
Example 1, except that 200 parts by weight of
methyltetracyclododecene (MTD) and 50 parts by weight of
dicyclopentadiene (DCP) were used instead of 2-norbornene, and the
amount of 1-hexene used was 0.70 parts by weight.
[0516] The weight average molecular weight (Mw) of the resulting
ring-open polymer (7) was 56,000, and the molecular weight
distribution (Mw/Mn) was 2.0.
[0517] The hydrogenation reaction was carried out in the same
manner as in Example 3 to obtain a hydrogenated ring-open polymer
(9).
(Properties of Polymer)
[0518] The degree of hydrogenation of the resulting hydrogenated
ring-open polymer (9) was 99.9%, the weight average molecular
weight (Mw) was 55,000, the molecular weight distribution (Mw/Mn)
was 3.1, the glass transition temperature was 140.degree. C., and a
melting point was not observed.
(Preparation of Resin Composition)
[0519] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (9) and the mixture
was kneaded using a twin-screw kneader (TEM35 manufactured by
Toshiba Machine Co., Ltd.) to obtain a pelletized resin
composition.
(Preparation of Resin Sheet)
[0520] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
220.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (9).
Comparative Example 4
Ring-Opening Polymerization and Hydrogenation Reaction
[0521] Polymerization was carried out in the same manner as in
Example 5, except that 0.06 parts by weight of 1-hexene was
used.
[0522] The weight average molecular weight (Mw) of the resulting
ring-open polymer (8) was 310,000, and the molecular weight
distribution (Mw/Mn) was 3.2. The hydrogenation reaction was
carried out in the same manner as in Example 1 to obtain a
hydrogenated norbornene ring-open polymer (10).
(Properties of Polymer)
[0523] The degree of hydrogenation of the resulting hydrogenated
ring-open polymer (10) was 99.0%, the weight average molecular
weight (Mw) was 300,200, the molecular weight distribution (Mw/Mn)
was 4.5, the isomerization ratio was 6%, and the melting point was
140.degree. C.
(Preparation of Resin Composition)
[0524] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (10) and the
mixture was kneaded using a twin-screw kneader (TEM35 manufactured
by Toshiba Machine Co., Ltd.) to obtain a pelletized resin
composition.
(Preparation of Resin Sheet)
[0525] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
150.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (10).
(Solubility Evaluation Test (c-Hex Solubility))
[0526] Solubility in cyclohexane was evaluated using the
hydrogenated ring-open polymers (1) to (10). The solubility was
judged by preparing a cyclohexane solution of the ring-open polymer
with a concentration of 20% at 70.degree. C. and cooling the
solution, while observing the temperature at which the polymer is
deposited with the naked eye. The results are shown in Table 2.
(Processability Evaluation Test (1))
[0527] Processability was evaluated using the hydrogenated
ring-open polymers (1) to (10). The processability was evaluated by
measuring the thickness of monolayer films (C1) (thickness: 100
.mu.m) obtained by molding the pellets of the hydrogenated
ring-open polymer (1) to (10) by T-die molding using a hanger
manifold T-die film melt extruding press machine (stationary type
manufactured by GSI Creos Corp.) equipped with a screw having a
screw diameter of 20 mm, a compression ratio of 2.5 or 3.1, and
L/D=30 under the following conditions. The results are shown in
Table 2.
[0528] Specifically, the film thickness was measured at 100 points
in the MD direction at intervals of 2.5 m using a micro gage to
calculate the standard deviation (a).
<Molding Conditions>
Die lip: 0.8 mm
[0529] Molten resin temperature: Tm of resin+40.degree. C. (resin
without a melting point: Tg+100.degree. C.)
Width of T-die: 300 mm
[0530] T-die temperature: Tm of resin+50.degree. C. (resin without
a melting point: Tg+110.degree. C.) Cooling roll: Tm of
resin-20.degree. C. (resin without a melting point: Tg-15.degree.
C.) Casting roll: Tm of resin-10.degree. C. (resin without a
melting point: Tg-5.degree. C.) Sheet roll-up rate: 2.5 m/min Screw
compression ratio: a screw with a compression ratio of 2.5 was used
for resins having no melting point, and a screw with a compression
ratio of 3.1 was used for other resins.
(Processability Evaluation Test (2))
[0531] The processability was evaluated by the film thickness
variation when monolayer films (C1) (thickness: 100 .mu.m) were
continuously produced for eight hours and the time before a die
line was generated (die line generation time) using the same
extruding press machine as used in the processability evaluation
test (1), of which the conditions were set so that the resin
pressure at the die portion was 3 MPa on average.
[0532] The same process conditions as in the processability
evaluation test (1) were employed, except that the molten resin
temperature and the T-die temperature shown in the following Table
1 were used when processing the hydrogenated ring-open polymers (1)
to (10).
TABLE-US-00001 TABLE 1 Hydrogenated ring-open Molten resin
temperature T-die temperature polymer (.degree. C.) (.degree. C.) 1
180 190 2 175 185 3 165 175 4 200 210 5 210 220 6 170 180 7 310 320
8 180 190 9 250 260 10 260 270
[0533] Specifically, at every one hour after the start of film
formation, the film thickness was measured at 10 points in the MD
direction at intervals of 2.5 m (total of 80 points) using a micro
gage to calculate the standard deviation. The time required for the
die line to be generated from the start of film formation was
measured by visually judging the occurrence of the die line.
(Measurement of Tensile Breaking Elongation)
[0534] Tensile breaking elongation was measured for each of the
resin sheets (1) to (10) obtained in the above. Tensile breaking
elongation was measured according to ISO 527 at a tensile velocity
of 200 mm/min using Autograph (AGS-5kNH, manufactured by Shimadzu
Corp.).
[0535] The measurement results are shown in Table 2.
(Evaluation Test of Stem Barrier Properties)
[0536] Moisture permeability of each of the sheets (1) to (10)
obtained above was evaluated. The moisture permeability was
measured according to JIS K7129 (method A) using a moisture
permeability tester (L80-5000 type, manufactured by LYSSY) under
conditions of a temperature of 40.degree. C. and humidity of 90%
RH. The measurement results are shown in Table 2. A small moisture
permeability (g/(m.sup.224 h)) indicates good steam barrier
properties.
(Evaluation of Oil Resistance)
[0537] Oil resistance of each of the sheets (1) to (10) obtained
above was evaluated. Critical stress to salad oil (manufactured by
Nisshin Oillio Group, Ltd.) was used for evaluation of the oil
resistance. After applying salad oil to the surface of a test
specimen with dimensions of 10 mm.times.100 mm.times.1 mm prepared
by heat-pressing, the test specimen was secured for one hour to a
curvature of an aluminum jig made by cutting an elliptic cylinder
with a height of 10 mm, a major ellipse axis of 200 mm and a minor
ellipse axis of 80 mm into four equal divisions, to observe whether
or not cracks were produced in the test specimen. All test
specimens were secured at fixed positions. For a test specimen in
which the cracks were generated, the crack generating positions
were measured taking the end of the test specimen on the low
curvature side at the time of securing as the starting point. The
results are shown in Table 2.
TABLE-US-00002 TABLE 2 c-Hex Processability Processability test (2)
Tensile Hydrogenated solubility test (1) Standard Die line breaking
Moisture ring-open (depositing Resin Standard deviation generation
elongation permeability Oil polymer temperature) sheet deviation
(.sigma.) (.sigma.) time (%) (g/(m.sup.2 24 h)) resistance Example
1 1 65.degree. C. 1 5 .mu.m 3 .mu.m .gtoreq.15 hrs 30 0.23 No
cracks 2 2 60.degree. C. 2 6 .mu.m 4 .mu.m .gtoreq.15 hrs 30 0.25
No cracks 3 3 40.degree. C. 3 6 .mu.m 4 .mu.m .gtoreq.15 hrs 35
0.30 No cracks 4 4 62.degree. C. 4 7 .mu.m 5 .mu.m 10 hrs 35 0.28
No cracks 5 5 62.degree. C. 5 8 .mu.m 5 .mu.m 10 hrs 25 0.31 No
cracks Comparative 1 6 69.degree. C. 6 10 .mu.m 7 .mu.m .gtoreq.15
hrs 8 0.24 Cracks at Example 75 mm 2 7 Not 7 10 .mu.m 8 .mu.m 2 hrs
15 0.78 No cracks dissolved Reference 1 8 69.degree. C. 8 18 .mu.m
10 .mu.m 13 hrs 25 0.23 No cracks Example Comparative 3 9
.ltoreq.25.degree. C. 9 5 .mu.m 4 .mu.m 6 hrs 40 0.98 Cracks at
Example 45 mm 4 10 35.degree. C. 10 15 .mu.m 7 .mu.m 3 hrs 25 0.28
No cracks
[0538] As shown in Table 2, the hydrogenated ring-open polymers (1)
to (5) of Examples 1 to 5 showed excellent solubility in
cyclohexane (c-Hex) and processability. The resin sheets (1) to (5)
of Examples 1 to 5 exhibited excellent mechanical properties as
indicated by the tensile breaking elongation of 25% or more, and
excellent steam barrier properties as indicated by the moisture
permeability of 0.31 g/(m.sup.224 h) or less. Furthermore, the
resin sheets (1) to (5) of Examples 1 to 5 exhibited excellent oil
resistance.
[0539] On the other hand, the hydrogenated ring-open polymers (6),
(7), and (8) of Comparative Examples 1 and 2 and Reference Example
1 showed poor solubility in cyclohexane as compared with the
hydrogenated ring-open polymers of the Examples.
[0540] In addition, the hydrogenated ring-open polymers (6), (7),
(8), and (10) of Comparative Examples 1, 2, and 4 and Reference
Example 1 showed poor processability as compared with the
hydrogenated ring-open polymers of the Examples.
[0541] Furthermore, the hydrogenated ring-open polymers (6), (7),
(8), and (10) of Comparative Examples 1, 2, and 4 and Reference
Example 1 had tensile breaking elongation of 25% or less, showing
the same or inferior mechanical properties as compared with the
hydrogenated ring-open polymers of the Examples. The moisture
permeability of the resin sheets (7) and (9) of Comparative
Examples 2 and 3 was 0.78 g/(m.sup.224 h) or more, indicating poor
steam barrier properties of these resin sheets as compared with the
resin sheets of the Examples. Furthermore, the resin sheets (6) and
(9) of Comparative Examples 1 and 3 exhibited poor oil
resistance.
[0542] Based on the above results, the hydrogenated ring-open
polymers and sheets of Examples 1 to 5 can be regarded as excellent
in all performance properties, including steam barrier properties,
heat resistance, oil resistance, mechanical properties,
transparency, and processability demanded in recent years in the
fields of information processing, food industries, medical
supplies, engineering works, and the like.
Example 6
Ring-Opening Copolymerization
[0543] A reactor was charged with 500 parts by weight of dehydrated
cyclohexane, 0.40 parts by weight of 1-hexene, 0.31 parts by weight
of diisopropyl ether, 0.20 parts by weight of triisobutylaluminum,
and 0.08 parts by weight of isobutyl alcohol at room temperature
under a nitrogen atmosphere. While maintaining the temperature at
55.degree. C., 245 parts by weight of 2-norbornene, 5 parts by
weight of methylnorbornene, and 15 parts by weight of a 1.0 wt %
solution of tungsten hexachloride in toluene were continuously
added in two hours to polymerize the monomers. The polymerization
conversion rate was about 100%.
[0544] The weight average molecular weight (Mw) of the resulting
ring-open polymer (9) was 103,000, and the molecular weight
distribution (Mw/Mn) was 1.9.
(Hydrogenation Reaction)
[0545] The polymerization reaction solution obtained above was
transferred to a pressure resistant hydrogenation reactor. After
the addition of 0.5 parts by weight of a nickel catalyst supported
by diatomaceous earth (T8400, nickel support rate: 58 wt %,
manufactured by Nissan-Sud-Chemie), the hydrogenation reaction was
carried out at 160.degree. C. under a hydrogen pressure of 4.5 MPa
for six hours. The reaction solution was filtered through a
stainless steel wire mesh filter, in which diatomaceous earth was
used as a filtration adjuvant, to remove the catalyst. The filtrate
was poured into 3000 parts by weight of isopropyl alcohol while
stirring to precipitate the hydrogenated product. After washing
with 500 parts by weight of acetone, the hydrogenated product was
dried in a vacuum dryer at 100.degree. C. under 0.13.times.10.sup.3
Pa for 48 hours to obtain 190 parts by weight of a hydrogenated
ring-open polymer (11).
(Properties of Polymer)
[0546] The degree of hydrogenation of the resulting hydrogenated
ring-open polymer (11) was 99.9%, the weight average molecular
weight (Mw) was 100,000, the molecular weight distribution (Mw/Mn)
was 2.9, the isomerization ratio was 8%, and the melting point was
136.degree. C.
(Preparation of Resin Composition)
[0547] 0.1 part by weight of
tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methan-
e (Irganox 1010 manufactured by Ciba Geigy, hereinafter referred to
as "Antioxidant A") was added to 100 parts by weight of a
hydrogenated ring-open polymer (11) and the mixture was kneaded
using a twin-screw kneader (TEM35 manufactured by Toshiba Machine
Co., Ltd.) to obtain a pelletized resin composition.
(Preparation of Resin Sheet)
[0548] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
150.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (11) with a thickness of 300 .mu.m.
Example 7
Ring-Opening Copolymerization
[0549] Polymerization was carried out in the same manner as in
Example 6, except that the amount of the monomers used was 240
parts by weight of 2-norbornene and 10 parts by weight of methyl
norbornene, and the amount of 1-hexene was 0.55 parts by weight.
The polymerization conversion rate was about 100%. The weight
average molecular weight (Mw) of the resulting ring-open polymer
(10) was 81,500, and the molecular weight distribution (Mw/Mn) was
1.8.
(Hydrogenation Reaction)
[0550] The polymerization reaction solution obtained above was
transferred to a pressure resistant hydrogenation reactor. After
the addition of 0.5 parts by weight of a nickel catalyst supported
by diatomaceous earth (T8400, nickel support rate: 58 wt %,
manufactured by Nissan-Sud-Chemie), the hydrogenation reaction was
carried out at 160.degree. C. under a hydrogen pressure of 4.5 MPa
for six hours. The reaction solution was filtered through a
stainless steel wire mesh filter, in which diatomaceous earth was
used as a filtration adjuvant, to remove the catalyst. The filtrate
was poured into 3000 parts by weight of isopropyl alcohol while
stirring to precipitate the hydrogenated product. After washing
with 500 parts by weight of acetone, the hydrogenated product was
dried in a vacuum dryer at 100.degree. C. under 0.13.times.10.sup.3
Pa for 48 hours to obtain 190 parts by weight of a hydrogenated
ring-open polymer (12).
(Properties of Polymer)
[0551] The degree of hydrogenation of the resulting hydrogenated
ring-open polymer (12) was 99.9%, the weight average molecular
weight (Mw) was 80,000, the molecular weight distribution (Mw/Mn)
was 2.9, the isomerization ratio was 8%, and the melting point was
133.degree. C.
(Preparation of Resin Composition)
[0552] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (12) and the
mixture was kneaded using a twin-screw kneader (TEM35 manufactured
by Toshiba Machine Co., Ltd.) to obtain a pelletized resin
composition.
(Preparation of Resin Sheet)
[0553] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
150.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (12) with a thickness of 300 .mu.m.
Example 8
Ring-Opening Copolymerization
[0554] An autoclave equipped with a stirrer was charged with 37.1
parts by weight of a 70 wt % 2-norbornene solution in toluene, 0.26
parts by weight of dicyclopentadiene, 0.020 parts by weight of
1-hexene, and 49.3 parts by weight of cyclohexane, and the mixture
was stirred. Then, a solution containing 0.023 parts by weight of
bis(tricyclohexylphosphine)benzylidyneruthenium (IV) dichloride in
8.6 parts by weight of toluene was added, and the reaction was
carried out at 60.degree. C. for 30 minutes. The polymerization
conversion rate was about 100%.
[0555] The weight average molecular weight (Mw) of the resulting
ring-open polymer (11) was 165,000, and the molecular weight
distribution (Mw/Mn) was 1.3.
(Hydrogenation Reaction)
[0556] 0.020 parts by weight of ethyl vinyl ether was added to the
polymer solution obtained above and the mixture was stirred,
followed by a hydrogenation reaction under a hydrogen pressure of
1.0 MPa at 150.degree. C. for 20 hours. After cooling to room
temperature, a suspension of 0.5 parts by weight of the activated
carbon in 10 parts by weight of cyclohexane was added and the
mixture was reacted under a hydrogen pressure of 1.0 MPa at
150.degree. C. for two hours. The reaction mixture was filtered
through a filter with a pore diameter of 0.2 .mu.m to remove the
activated carbon. The reaction solution was poured into a large
amount of isopropanol to cause the polymer to completely
precipitate. The precipitate was collected by filtration. After
washing with acetone, the hydrogenated product was dried in a
vacuum dryer at 100.degree. C. under 0.13.times.10.sup.3 Pa for 48
hours to obtain a hydrogenated ring-open polymer (13).
(Properties of Polymer)
[0557] The degree of hydrogenation of the resulting hydrogenated
ring-open polymer (13) was 99.9%, the weight average molecular
weight (Mw) was 160,000, the molecular weight distribution (Mw/Mn)
was 1.8, the isomerization ratio was 0%, and the melting point was
139.degree. C.
(Preparation of Resin Composition)
[0558] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (13) and the
mixture was kneaded using a twin-screw kneader to obtain a
pelletized resin composition.
(Preparation of Resin Sheet)
[0559] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
150.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (13) with a thickness of 300 .mu.m.
Example 9
Ring-Opening Copolymerization and Hydrogenation Reaction
[0560] A polymerization reaction was carried out in the same manner
as in Example 6 except that the amount of the monomers used was
227.5 parts by weight of 2-norbornene and 22.5 parts by weight of
methylnorbornene, and the amount of other components was 0.4 parts
by weight of 1-hexene, 0.40 parts by weight of diisopropyl ether,
0.27 parts by weight of triisobutylaluminum, 0.10 part by weight of
isobutyl alcohol, and 20 parts by weight of a 1.0 wt % tungsten
hexachloride solution in toluene. The polymerization conversion
rate was about 100%.
[0561] The weight average molecular weight (Mw) of the resulting
ring-open polymer (12) was 101,000, and the molecular weight
distribution (Mw/Mn) was 2.8.
[0562] The hydrogenation reaction was carried out in the same
manner as in Example 6 to obtain a hydrogenated norbornene
ring-open polymer (14).
(Properties of Polymer)
[0563] The degree of hydrogenation of the resulting ring-open
polymer (14) was 99.9%, the weight average molecular weight (Mw)
was 98,800, the molecular weight distribution (Mw/Mn) was 3.8, the
isomerization ratio was 7%, and the melting point was 114.degree.
C.
(Preparation of Resin Composition)
[0564] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (14) and the
mixture was kneaded using a twin-screw kneader (TEM35 manufactured
by Toshiba Machine Co., Ltd.) to obtain a pelletized resin
composition.
(Preparation of Resin Sheet)
[0565] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
145.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (14) with a thickness of 300 .mu.m.
Example 10
Ring-Opening Copolymerization and Hydrogenation Reaction
[0566] A polymerization reaction was carried out in the same manner
as in Example 6 except that the amount of the monomers used was 240
parts by weight of 2-norbornene and 10 parts by weight of
dicyclopentadiene, and the amount of other components was 0.55
parts by weight of 1-hexene, 0.40 parts by weight of diisopropyl
ether, 0.27 parts by weight of triisobutylaluminum, 0.10 part by
weight of isobutyl alcohol, and 20 parts by weight of a 1.0 wt %
tungsten hexachloride solution in toluene. The polymerization
conversion rate was about 100%.
[0567] The weight average molecular weight (Mw) of the resulting
ring-open polymer (13) was 83,000, and the molecular weight
distribution (Mw/Mn) was 2.7.
[0568] The hydrogenation reaction was carried out in the same
manner as in Example 6 to obtain 190 parts by weight of a
hydrogenated norbornene ring-open polymer (15).
(Properties of Polymer)
[0569] The degree of hydrogenation of the resulting ring-open
polymer (15) was 99.9%, the weight average molecular weight (Mw)
was 81,300, the molecular weight distribution (Mw/Mn) was 3.8, the
isomerization ratio was 9%, and the melting point was 134.degree.
C.
(Preparation of Resin Composition)
[0570] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (15) and the
mixture was kneaded using a twin-screw kneader (TEM35 manufactured
by Toshiba Machine Co., Ltd.) to obtain a pelletized resin
composition.
(Preparation of Resin Sheet)
[0571] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
145.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (15) with a thickness of 300 .mu.m.
Example 11
[0572] A polymerization reaction was carried out in the same manner
as in Example 6 except that the amount of the monomers used was 240
parts by weight of 2-norbornene and 10 parts by weight of
dicyclopentadiene, and the amount of other components was 0.15
parts by weight of 1-hexene, 0.40 parts by weight of diisopropyl
ether, 0.27 parts by weight of triisobutylaluminum, 0.10 part by
weight of isobutyl alcohol, and 20 parts by weight of a 1.0 wt %
tungsten hexachloride solution in toluene. The polymerization
conversion rate was about 100%.
[0573] The weight average molecular weight (Mw) of the resulting
ring-open polymer (14) was 140,000, and the molecular weight
distribution (Mw/Mn) was 7.1.
[0574] The hydrogenation reaction was carried out in the same
manner as in Example 6 to obtain 190 parts by weight of a
hydrogenated norbornene ring-open polymer (16).
(Properties of Polymer)
[0575] The degree of hydrogenation of the resulting hydrogenated
ring-open polymer (16) was 99.9%, the weight average molecular
weight (Mw) was 137,000, the molecular weight distribution (Mw/Mn)
was 7.8, the isomerization ratio was 9%, and the melting point was
134.degree. C.
(Preparation of Resin Composition)
[0576] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (16) and the
mixture was kneaded using a twin-screw kneader (TEM35 manufactured
by Toshiba Machine Co., Ltd.) to obtain a pelletized resin
composition.
(Preparation of Resin Sheet)
[0577] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
145.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (16) with a thickness of 300 .mu.m.
Comparative Example 5
Ring-Opening Copolymerization and Hydrogenation Reaction
[0578] Polymerization was carried out in the same manner as in
Example 8, except that 200 parts by weight of
methyltetracyclododecene (MTD) and 50 parts by weight of
dicyclopentadiene (DCP) were used instead of 2-norbornene, and the
amount of 1-hexene used was 0.40 parts by weight. The
polymerization conversion rate was about 100%.
[0579] The weight average molecular weight (Mw) of the resulting
ring-open polymer (15) was 56,000, and the molecular weight
distribution (Mw/Mn) was 3.7.
[0580] The hydrogenation reaction was carried out in the same
manner as in Example 6, except that the amount of the nickel
catalyst supported by diatomaceous earth was 3 parts by weight, to
obtain a hydrogenated norbornene ring-open polymer (17).
(Properties of Polymer)
[0581] The degree of hydrogenation of the resulting hydrogenated
ring-open polymer (17) was 99.9%, the weight average molecular
weight (Mw) was 55,000, the molecular weight distribution (Mw/Mn)
was 2.9, the glass transition temperature was 140.degree. C., and a
melting point was not observed.
(Preparation of Resin Composition)
[0582] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (17) and the
mixture was kneaded using a twin-screw kneader (TEM35 manufactured
by Toshiba Machine Co., Ltd.) to obtain pellets.
(Preparation of Resin Sheet)
[0583] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
220.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (17) with a thickness of 300 .mu.m.
Comparative Example 6
Ring-Opening Copolymerization and Hydrogenation Reaction
[0584] A polymerization reaction was carried out in the same manner
as in Example 6 except for using 222.5 parts by weight of
2-norbornene and 27.5 parts by weight of tetracyclododecene as
monomers, and 0.07 parts by weight of 1-hexene, 0.4 parts by weight
of diisopropyl ether, 0.27 parts by weight of triisobutylaluminum,
0.10 part by weight of isobutyl alcohol, and 20 parts by weight of
a 1.0 wt % tungsten hexachloride solution in toluene. The
polymerization conversion rate was about 100%.
[0585] The weight average molecular weight (Mw) of the resulting
ring-open polymer (16) was 319,500, and the molecular weight
distribution (Mw/Mn) was 3.4.
[0586] The hydrogenation reaction was carried out in the same
manner as in Example 6, except that the amount of the nickel
catalyst supported by diatomaceous earth was 3 parts by weight, to
obtain a hydrogenated norbornene ring-open polymer (18).
(Properties of Polymer)
[0587] The degree of hydrogenation of the resulting hydrogenated
ring-open polymer (18) was 99.0%, the weight average molecular
weight (Mw) was 315,000, the molecular weight distribution (Mw/Mn)
was 4.9, the isomerization ratio was 9%, and the melting point was
100.degree. C.
(Preparation of Resin Composition)
[0588] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (18) and the
mixture was kneaded using a twin-screw kneader (TEM35 manufactured
by Toshiba Machine Co., Ltd.) to obtain a pelletized resin
composition.
(Preparation of Resin Sheet)
[0589] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
135.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (18) with a thickness of 300 .mu.m.
Reference Example 2
[0590] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (8) obtained in
Reference Example 1 and the mixture was kneaded using a twin-screw
kneader (TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain
a pelletized resin composition.
(Preparation of Resin Sheet)
[0591] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
150.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (19) with a thickness of 300 .mu.m.
Comparative Example 7
[0592] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (7) obtained in
Comparative Example 2 and the mixture was kneaded using a
twin-screw kneader (TEM35 manufactured by Toshiba Machine Co.,
Ltd.) to obtain a pelletized resin composition.
(Preparation of Resin Sheet)
[0593] The pellets were pressed by a vacuum heat-press apparatus
(manufactured by Imoto Factory Co., Ltd.) at a die temperature of
280.degree. C. under a pressure of 8 MPa for five minutes, using a
mold die with a thickness of 1 mm, a length of 200 mm, and a width
of 100 mm, with one side being mirror plane processed, and cooled
to room temperature at a cooling rate of 0.5.degree. C./min to
obtain a resin sheet (20).
(Solubility Evaluation Test (c-Hex Solubility))
[0594] Solubility in cyclohexane was evaluated using the
hydrogenated ring-open polymers (11) to (18), (8), and (7). The
solubility was judged by preparing a cyclohexane solution of the
ring-open polymer with a concentration of 20% at 70.degree. C. and
cooling the solution, while observing the temperature at which the
polymer was deposited with the naked eye. The results are shown in
Table 3.
(Processability Evaluation Test (1))
[0595] Processability was evaluated using the hydrogenated
ring-open polymers (11) to (18), (8), and (7). The processability
was evaluated by measuring the thickness of monolayer films (C1)
(thickness: 100 .mu.m) obtained by molding the pellets of the
hydrogenated ring-open polymer (11) to (18), (8), and (7) by T-die
molding using a hanger manifold T-die film melt extruding press
machine (stationary type manufactured by GSI Creos Corp.) equipped
with a screw having a screw diameter of 20 mm, a compression ratio
of 2.5 or 3.1, and L/D=30 under the following conditions. The
results are shown in Table 4.
[0596] Specifically, the film thickness was measured at 100 points
in the MD direction at intervals of 2.5 m using a micro gage to
calculate the standard deviation (.sigma.).
<Molding Conditions>
Die lip: 0.8 mm
[0597] Molten resin temperature: Tm of resin+40.degree. C. (resin
without a melting point: Tg+100.degree. C.)
Width of T-die: 300 mm
[0598] T-die temperature: Tm of resin+50.degree. C. (resin without
a melting point: Tg+110.degree. C.) Cooling roll: Tm of
resin-20.degree. C. (resin without a melting point: Tg-15.degree.
C.) Casting roll: Tm of resin-10.degree. C. (resin without a
melting point: Tg-5.degree. C.) Sheet roll-up rate: 2.5 m/min Screw
compression ratio: a screw with a compression ratio of 2.5 was used
for resins having no melting point, and a screw with a compression
ratio of 3.1 was used for other resins.
(Processability Evaluation Test (2))
[0599] The processability were evaluated by the film thickness
variation when monolayer films (C1) (thickness: 100 .mu.m) were
continuously produced for eight hours and the time before a die
line was generated (die line generation time) using the same
extruding press machine as used in the processability evaluation
test (1), of which the conditions were set so that the resin
pressure at the die portion is 3 MPa on average.
[0600] The same process conditions as in the processability
evaluation test (1) were employed, except that the molten resin
temperature and the T-die temperature shown in the following Table
3 were used when processing the hydrogenated ring-open polymers
(11) to (18), (8), and (7).
TABLE-US-00003 TABLE 3 Hydrogenated ring-open Molten resin
temperature T-die temperature (co)polymer (.degree. C.) (.degree.
C.) 11 170 180 12 170 180 13 190 200 14 155 165 15 175 185 16 190
200 17 240 250 18 235 245 8 175 185 7 315 325
[0601] Specifically, at every one hour after the start of film
formation, the film thickness was measured at 10 points in the MD
direction at intervals of 2.5 m (total of 80 points) using a micro
gage to calculate the standard deviation. The time required for the
die line to be generated from the start of film formation was
measured by visually judging the occurrence of the die line.
[0602] The term "die line" refers to a streak, observable with the
naked eye, continuously generated along the direction of extrusion
of the resin at the position of the molded article corresponding to
the specific position of the die. Specifically, the die line is a
streak formed on the surface of the molded article consisting of
irregularities (concaves and convexes) with a height of about 0.3
.mu.m to 100 .mu.m. Smaller concaves and convexes cannot be
observed with the naked eye.
(Measurement of Tensile Breaking Elongation)
[0603] Tensile breaking elongation was measured for each of the
resin sheets (11) to (20) obtained in the above. Tensile breaking
elongation was measured according to ISO 527 at a tensile velocity
of 200 mm/min using an Autograph (AGS-5kNH, manufactured by
Shimadzu Corp.). The measurement results are shown in Table 4.
(Evaluation Test of Steam Barrier Properties)
[0604] Moisture permeability of each of the sheets (11) to (20)
obtained above was evaluated. The moisture permeability was
measured according to JIS K7129 (method A) using a moisture
permeability tester (L80-5000 type, manufactured by LYSSY) under
conditions of a temperature of 40.degree. C. and humidity of 90%
RH. The measurement results are shown in Table 4. A small moisture
permeability (g/(m.sup.224 h)) indicates good steam barrier
properties.
(Evaluation of Oil Resistance)
[0605] Oil resistance of each of the sheets (11) to (20) obtained
above was evaluated. Critical stress to salad oil (manufactured by
Nisshin Oillio Group, Ltd.) was used for evaluation of the oil
resistance. After applying salad oil to the surface of a test
specimen with dimensions of 10 mm.times.100 mm.times.1 mm prepared
by heat-pressing, the test specimen was secured for one hour to a
curvature of an aluminum jig made by cutting an elliptic cylinder
with a height of 10 mm, a major ellipse axis of 200 mm and a minor
ellipse axis of 80 mm into four equal divisions, to observe whether
or not cracks were produced in the test specimen. All test
specimens were secured at fixed positions. For a test specimen in
which the cracks were generated, the crack generating positions
were measured taking the end of the test specimen on the low
curvature side at the time of securing as the starting point. The
results are shown in Table 4.
(Measurement of Haze)
[0606] Haze of each of the sheets (11) to (20) obtained above was
measured. Samples with a thickness of 300 .mu.m were prepared and
the haze was measured using a haze meter (NDH2000 manufactured by
Nippon Denshoku Co., Ltd.). The measurement results are shown in
Table 4.
TABLE-US-00004 TABLE 4 Processability c-Hex Processability
evaluation (2) Tensile Hydrogenated solubility evaluation (1)
Standard Time breaking Moisture ring-open (deposition Resin
Standard deviation before die elongation permeability Haze Oil
polymer temperature) sheet deviation (.sigma.) (.sigma.) line
formation (%) (g/(m.sup.2 24 h)) (%) resistance Example 6 11
62.degree. C. 11 6 .mu.m 3 .mu.m .gtoreq.15 hrs 33 0.23 30.1 No
cracks 7 12 57.degree. C. 12 8 .mu.m 4 .mu.m .gtoreq.15 hrs 35 0.24
28.0 No cracks 8 13 60.degree. C. 13 6 .mu.m 4 .mu.m 10 hrs 35 0.24
27.2 No cracks 9 14 49.degree. C. 14 9 .mu.m 4 .mu.m .gtoreq.15 hrs
37 0.40 22.2 No cracks 10 15 62.degree. C. 15 8 .mu.m 4 .mu.m
.gtoreq.15 hrs 30 0.30 26.0 No cracks 11 16 58.degree. C. 16 8
.mu.m 4 .mu.m .gtoreq.15 hrs 35 0.30 29.0 No cracks Comparative 5
17 .ltoreq.25.degree. C. 17 5 .mu.m 4 .mu.m .gtoreq.15 hrs 40 0.98
0.9 Cracks at Example 45 mm 6 18 40.degree. C. 18 15 .mu.m 7 .mu.m
3 hrs 25 0.78 21.4 No cracks Reference 2 8 69.degree. C. 19 18
.mu.m 10 .mu.m 13 hrs 25 0.23 41.0 No cracks Example Comparative 7
7 did not 20 10 .mu.m 8 .mu.m 2 hrs 15 0.78 28.0 No cracks Example
dissolve
[0607] As shown in Table 4, the hydrogenated ring-open polymers
(11) to (16) of Examples 6 to 11 and the hydrogenated ring-open
polymers (18) and (8) of Comparative Example 6 and Reference
Example 2 showed excellent solubility. On the other hand, the
hydrogenated ring-open polymer (7) of Comparative Example 7 showed
poor solubility.
[0608] The hydrogenated ring-open polymers (11) to (16) of Examples
6 to 11 and the hydrogenated ring-open polymer (17) of Comparative
Example 5 showed excellent processability as compared with the
hydrogenated ring-open polymers (18), (8), and (7) of Comparative
Examples 6 and 7, and Reference Example 2.
[0609] The resin sheets (11) to (16) of Examples 6 to 11 exhibited
excellent mechanical properties as indicated by the tensile
breaking elongation of 30% or more. On the other hand, the resin
sheets (18) to (20) of Comparative Examples 6, 7 and Reference
Example 2 exhibited poor mechanical properties as indicated by the
tensile breaking elongation of 25% or less.
[0610] The moisture permeability of the resin sheets (11) to (16)
of Examples 6 to 11 and the resin sheet (19) of Reference Example 2
was 0.40 g/(m.sup.224 h) or less, indicating excellent steam
barrier properties. The moisture permeability of the resin sheets
(17), (18), and (20) of Comparative Examples 5, 6, and 7 was 0.78
g/(m.sup.224 h) or more, indicating poor steam barrier properties
of these resin sheets.
[0611] The haze of the resin sheets (11) to (16) of Examples 6 to
11 and the resin sheets (17), (18), and (20) of Comparative
Examples 5, 6, and 7 was 30.1% or less. On the other hand, the haze
of resin sheet (19) of Reference Example 2 was 41.0% indicating
poor transparency.
[0612] The resin sheets (11) to (16) of Examples 6 to 11 and the
resin sheets (18) to (20) of Comparative Examples 6 and 7, and
Reference Example 2 exhibited excellent oil resistance. On the
other hand, the resin sheet (17) of Comparative Example 5 exhibited
poor oil resistance.
[0613] Based on the above results, the hydrogenated ring-open
polymers and resin sheets of Examples 6 to 11 can be regarded as
excellent in all performance, including steam barrier properties,
heat resistance, oil resistance, mechanical properties,
transparency, and processability demanded in recent years in the
fields of information processing, food industries, medical
supplies, engineering works, and the like.
Example 12
[0614] 0.1 part by weight of an antioxidant
(tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]metha-
ne (Irganox 1010 manufactured by Ciba Geigy)) was added to 100
parts by weight of the hydrogenated ring-open polymer (1) obtained
in Example 1, and the mixture was kneaded using a twin-screw
kneader (TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain
a pelletized resin composition.
(Preparation of Tube Sheet)
[0615] The pellets were processed by an inflation machine
(manufactured by Sumitomo Heavy Industries Modern, Ltd.) to produce
a tube sheet (A) with a thickness of 250 .mu.m under the conditions
of a lip clearance of 2.5 mm, a drawing speed of 8 m/min, and a die
temperature of 190.degree. C.
Example 13
[0616] 0.1 part by weight of an antioxidant
(tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]metha-
ne (Irganox 1010 manufactured by Ciba Geigy)) was added to 100
parts by weight of the hydrogenated ring-open polymer (11) obtained
in Example 6, and the mixture was kneaded using a twin-screw
kneader (TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain
a pelletized resin composition.
(Preparation of Tube Sheet)
[0617] The pellets and low density polyethylene (Novatech SF720:
density 0.928 g/cm.sup.3, manufactured by Japan Polyethylene Corp.)
were processed by an inflation machine (manufactured by Sumitomo
Heavy Industries Modern, Ltd.) to produce a tube sheet (B) with a
thickness of 250 .mu.m, consisting of a layer of the hydrogenated
ring-open polymer (11) (thickness: 30 .mu.m) and a layer of the low
density polyethylene (thickness: 220 .mu.m) under the conditions of
a lip clearance of 2.5 mm, a drawing speed of 8 m/min, and a die
temperature of 190.degree. C.
Example 14
[0618] 0.1 part by weight of an antioxidant
(tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]metha-
ne (Irganox 1010 manufactured by Ciba Geigy)) was added to 100
parts by weight of the hydrogenated ring-open polymer (14) obtained
in Example 9, and the mixture was kneaded using a twin-screw
kneader (TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain
a pelletized resin composition.
(Preparation of Tube Sheet)
[0619] The pellets and low density polyethylene (Novatech SF720:
density 0.928 g/cm.sup.3, manufactured by Japan Polyethylene Corp.)
were processed by an inflation machine (manufactured by Sumitomo
Heavy Industries Modern, Ltd.) to produce a tube sheet (C) with a
thickness of 250 .mu.m, consisting of a layer of the hydrogenated
ring-open polymer (14) (thickness: 30 .mu.m) and a layer of the low
density polyethylene (thickness: 220 .mu.m) under the conditions of
a lip clearance of 2.5 mm, a drawing speed of 8 m/min, and a die
temperature of 190.degree. C.
Example 15
[0620] 0.1 part by weight of an antioxidant
(tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]metha-
ne (Irganox 1010 manufactured by Ciba Geigy)) was added to 100
parts by weight of the hydrogenated ring-open polymer (5) obtained
in Example 5, and the mixture was kneaded using a twin-screw
kneader (TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain
a pelletized resin composition.
(Preparation of Tube Sheet)
[0621] The pellets and low density polyethylene (Novatech SF720:
density 0.928 g/cm.sup.3, manufactured by Japan Polyethylene Corp.)
were processed by an inflation machine (manufactured by Sumitomo
Heavy Industries Modern, Ltd.) to produce a tube sheet (D) with a
thickness of 250 .mu.m, consisting of a layer of the hydrogenated
ring-open polymer (5) (thickness: 30 .mu.m) and a layer of the low
density polyethylene (thickness: 220 .mu.m) under the conditions of
a lip clearance of 2.5 mm, a drawing speed of 8 m/min, and a die
temperature of 190.degree. C.
Example 16
[0622] 0.1 part by weight of an antioxidant
(tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]metha-
ne (Irganox 1010 manufactured by Ciba Geigy)) was added to 100
parts by weight of the hydrogenated ring-open polymer (3) obtained
in Example 3, and the mixture was kneaded using a twin-screw
kneader (TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain
a pelletized resin composition.
(Preparation of Tube Sheet)
[0623] The pellets and low density polyethylene (Novatech SF720:
density 0.928 g/cm.sup.3, manufactured by Japan Polyethylene Corp.)
were processed by an inflation machine (manufactured by Sumitomo
Heavy Industries Modern, Ltd.) to produce a tube sheet (E) with a
thickness of 250 .mu.m, consisting of a layer of the hydrogenated
ring-open polymer (3) (thickness: 30 .mu.m) and a layer of the low
density polyethylene (thickness: 220 .mu.m) under the conditions of
a lip clearance of 2.5 mm, a drawing speed of 8 m/min, and a die
temperature of 190.degree. C.
Example 17
[0624] 0.1 part by weight of an antioxidant
(tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]metha-
ne (Irganox 1010 manufactured by Ciba Geigy)) was added to 100
parts by weight of the hydrogenated ring-open polymer (15) obtained
in Example 10, and the mixture was kneaded using a twin-screw
kneader (TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain
a pelletized resin composition.
(Preparation of Tube Sheet)
[0625] The pellets of the hydrogenated ring-open polymer (15) were
processed by an inflation machine (manufactured by Sumitomo Heavy
Industries Modern, Ltd.) to produce a tube sheet (F) with a
thickness of 250 .mu.m under the conditions of a lip clearance of
2.5 mm, a drawing speed of 8 m/min, and a die temperature of
190.degree. C.
Example 18
Preparation of Tube Sheet
[0626] The pellets of the hydrogenated ring-open polymer (15) and
low density polyethylene (Novatech SF720: density 0.928 g/cm.sup.3,
manufactured by Japan Polyethylene Corp.) were processed by an
inflation machine (manufactured by Sumitomo Heavy Industries
Modern, Ltd.) to produce a tube sheet (G) with a thickness of 250
.mu.m, consisting of a layer of the hydrogenated ring-open polymer
(15) (thickness: 30 .mu.m) and a layer of the low density
polyethylene (thickness: 220 .mu.m) under the conditions of a lip
clearance of 2.5 mm, a drawing speed of 8 m/min, and a die
temperature of 190.degree. C.
Example 19
Preparation of Tube Sheet
[0627] The pellets of the hydrogenated ring-open polymer (1) and
low density polyethylene (Novatech SF720: density 0.928 g/cm.sup.3,
manufactured by Japan Polyethylene Corp.) were processed by an
inflation machine (manufactured by Sumitomo Heavy Industries
Modern, Ltd.) to produce a tube sheet (H) with a thickness of 250
.mu.m, consisting of three layers of a low density polyethylene
layer (thickness:110 .mu.m), a hydrogenated ring-open polymer (1)
layer (thickness: 30 .mu.m), and a low density polyethylene layer
(thickness: 110 .mu.m) under the conditions of a lip clearance of
2.5 mm, a drawing speed of 8 m/min, and a die temperature of
190.degree. C.
Example 20
[0628] 0.1 part by weight of an antioxidant
(tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]metha-
ne (Irganox 1010 manufactured by Ciba Geigy)) was added to 100
parts by weight of the hydrogenated ring-open polymer (8) obtained
in Reference Example 1, and the mixture was kneaded using a
twin-screw kneader (TEM35 manufactured by Toshiba Machine Co.,
Ltd.) to obtain pellets.
(Preparation of Tube Sheet)
[0629] The pellets of the hydrogenated ring-open polymer (8) and
low density polyethylene (Novatech SF720: density 0.928 g/cm.sup.3,
manufactured by Japan Polyethylene Corp.) were processed by an
inflation machine (manufactured by Sumitomo Heavy Industries
Modern, Ltd.) to produce a tube sheet (I) with a thickness of 250
.mu.m, consisting of a layer of the hydrogenated ring-open polymer
(8) (thickness: 30 .mu.m) and a layer of the low density
polyethylene (thickness: 220 .mu.m) under the conditions of a lip
clearance of 2.5 mm, a drawing speed of 8 m/min, and a die
temperature of 190.degree. C.
Comparative Example 8
[0630] 0.1 part by weight of an antioxidant
(tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]metha-
ne (Irganox 1010 manufactured by Ciba Geigy)) was added to 100
parts by weight of the hydrogenated ring-open polymer (18) obtained
in Comparative Example 6, and the mixture was kneaded using a
twin-screw kneader (TEM35 manufactured by Toshiba Machine Co.,
Ltd.) to obtain a pelletized resin composition.
(Preparation of Tube Sheet)
[0631] The pellets of the hydrogenated ring-open polymer (17) and
low density polyethylene (Novatech SF720: density 0.928 g/cm.sup.3,
manufactured by Japan Polyethylene Corp.) were processed by an
inflation machine (manufactured by Sumitomo Heavy Industries
Modern, Ltd.) to produce a tube sheet (J) with a thickness of 250
.mu.m, consisting of a layer of the hydrogenated ring-open polymer
(17) (thickness: 30 .mu.m) and a layer of the low density
polyethylene (thickness: 220 .mu.m) under the conditions of a lip
clearance of 2.5 mm, a drawing speed of 8 m/min, and a die
temperature of 190.degree. C.
Comparative Example 9
[0632] 0.1 part by weight of an antioxidant
(tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]metha-
ne (Irganox 1010 manufactured by Ciba Geigy)) was added to 100
parts by weight of the hydrogenated ring-open polymer (17) obtained
in Comparative Example 5, and the mixture was kneaded using a
twin-screw kneader (TEM35 manufactured by Toshiba Machine Co.,
Ltd.) to obtain a pelletized resin composition.
(Preparation of Tube Sheet)
[0633] The pellets of the hydrogenated ring-open polymer (17) and
low density polyethylene (Novatech SF720: density 0.928 g/cm.sup.3,
manufactured by Japan Polyethylene Corp.) were processed by an
inflation machine (manufactured by Sumitomo Heavy Industries
Modern, Ltd.) to produce a tube sheet (K) with a thickness of 250
.mu.m, consisting of a layer of the hydrogenated ring-open polymer
(16) (thickness: 30 .mu.m) and a layer of the low density
polyethylene (thickness: 220 .mu.m) under the conditions of a lip
clearance of 2.5 mm, a drawing speed of 8 m/min, and a die
temperature of 260.degree. C.
Comparative Example 10
[0634] 0.1 part by weight of an antioxidant
(tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]metha-
ne (Irganox 1010 manufactured by Ciba Geigy)) was added to 100
parts by weight of the hydrogenated ring-open polymer (7) obtained
in Comparative Example 2, and the mixture was kneaded using a
twin-screw kneader (TEM35 manufactured by Toshiba Machine Co.,
Ltd.) to obtain pellets.
(Preparation of Tube Sheet)
[0635] The pellets and low density polyethylene (Novatech SF720:
density 0.928 g/cm.sup.3, manufactured by Japan Polyethylene Corp.)
were processed by an inflation machine (manufactured by Sumitomo
Heavy Industries Modern, Ltd.) to produce a tube sheet (L) with a
thickness of 250 pin, consisting of a layer of the hydrogenated
ring-open polymer (7) (thickness: 30 .mu.m) and a layer of the low
density polyethylene (thickness: 220 .mu.m) under the conditions of
a lip clearance of 2.5 mm, a drawing speed of 8 m/min, and a die
temperature of 285.degree. C.
Comparative Example 11
Preparation of Tube Sheet
[0636] A low density polyethylene (Novatech SF720: density 0.928
g/cm.sup.3, manufactured by Japan Polyethylene Corp.) was processed
by an inflation machine (manufactured by Sumitomo Heavy Industries
Modern, Ltd.) to produce a tube sheet (M) made of the low density
polyethylene with a thickness of 250 .mu.m under the conditions of
a lip clearance of 2.5 mm, a drawing speed of 8 m/min, and a die
temperature of 190.degree. C.
[0637] The number of hydrogenated ring-open polymers of Examples 12
to 20 and Comparative Examples 8 to 11, the composition, Mw, Mw/Mn,
hydrogenation degree (%), isomerization ratio (%), melting point,
and the tube sheet constitution are shown in Table 5.
TABLE-US-00005 TABLE 5 Hydrogenated ring-open polymer Melting Tube
Hydrogenation Isomerization point Layer sheet No. Composition Mw
Mw/Mn rate (%) rate (%) (.degree. C.) constitution Example 12 A 1
NB 100 82200 2.9 99.9 5 140 A 13 B 11 NB/MNB = 98/2 100000 2.9 99.9
8 136 PE/B 14 C 14 NB/MNB = 91/9 98800 3.8 99.9 7 114 PE/C 15 D 5
NB 100 185000 4.4 99.9 10 136 PE/D 16 E 3 NB 100 81600 2.8 99.9 35
125 PE/E 17 F 15 NB/DCP = 96/4 81300 3.8 99.9 9 134 F 18 G 15
NB/DCP = 96/4 81300 3.8 99.9 9 134 PE/F 19 H 1 NB 100 82200 2.9
99.9 5 140 PE/A/PE 20 I 8 NB 100 64200 1.3 99.75 0 143 PE/G
Comparative 8 J 18 NB/TCD = 89/11 315000 4.9 99.0 9 100 PE/H
Example 9 K 17 MTD/DCP = 80/20 55000 2.9 99.9 -- -- PE/I 10 L 7 DCP
100 -- -- -- -- 273 PE/J 11 M -- -- -- -- -- -- -- PE PE =
Polyethylene
[0638] The thickness fluctuation, moisture permeability at
40.degree. C., moisture permeability at 50.degree. C., modulus of
elasticity, strain at the time of crack generation, and haze change
when salad oil was applied were measured and evaluated using the
tube sheets (A) to (M). In the measurement and evaluation of the
thickness fluctuation, moisture permeability at 40.degree. C.,
moisture permeability at 50.degree. C., and haze change when salad
oil was applied, a sheet with a thickness of 250 .mu.m produced by
cutting the side of the tube sheet was used. The modulus of
elasticity and strain at the time of crack generation were
evaluated using a dumbbell form test specimen 1B type with a
thickness of 250 .mu.m based on ISO527. The results are shown in
Table 6.
TABLE-US-00006 TABLE 6 Strain at the Haze change Thickness Modulus
of time of crack before and after Tube Layer Thickness standard
Steam barrier properties elasticity generation salad oil sheet
constitution (.mu.m) deviation 40.degree. C. .times. 90% RH
50.degree. C. .times. 90% RH (MPa) (%) application* Example 12 A A
250 6.2 0.09 0.23 420 27 0.86 13 B PE/B 220/30 6.5 0.42 1.48 362 30
0.94 14 C PE/C 220/30 6.9 0.52 1.78 360 37 0.94 15 D PE/D 220/30
7.4 0.47 1.68 358 25 0.97 16 E PE/E 220/30 6.5 0.44 1.50 360 34
0.94 17 F F 250 6.4 0.18 0.68 390 32 0.86 18 G PE/F 220/30 7.0 0.52
1.72 342 32 0.94 19 H PE/A/PE 110/30/110 6.4 0.43 1.49 358 28 1.00
20 I PE/G 220/30 7.9 0.46 1.58 386 24 0.86 Comparative 8 J PE/H
220/30 7.8 0.68 2.48 380 28 0.98 Example 9 K PE/J 220/30 13.4 0.87
3.65 680 28 0.44 10 L PE/K 220/30 18.4 0.76 2.86 720 17 0.90 11 M
PE 250 6.4 1.00 6.40 350 .gtoreq.50 1.00 *Haze without treating
with salad oil/haze after salad oil attachment
[0639] As shown in Table 6, the tube sheets (A) to (I), (J), and
(M) of Examples 12 to 20 and Comparative Examples 8 and 11 had
small thickness standard deviation values, indicating a small
thickness fluctuation. On the other hand, the tube sheets (K) and
(L) of Comparative Examples 9 and 10 had comparatively large
thickness standard deviation values, indicating their comparatively
large thickness fluctuation.
[0640] The tube sheets (A) to (I) of Examples 12 to 20 showed
excellent steam barrier properties particularly at a high
temperature (50.degree. C.). The tube sheets (J) to (M) of
Comparative Examples 8 to 11 showed poor steam barrier properties
particularly at a high temperature (50.degree. C.).
[0641] The tube sheets (A) to (I) of Examples 12 to 20 and the tube
sheets (J) and (M) of Comparative Examples 8 and 11 had a modulus
of elasticity of 420 MPa or less, indicating their excellent
pliability. On the other hand, the tube sheets (K) and (L) of
Comparative Examples 9 and 10 had modulus of elasticity of 680 MPa
or more, indicating their poor pliability.
[0642] The tube sheets (B), (C), and (E) to (G) of Examples 13, 14,
and 16 to 18 exhibited particularly excellent mechanical properties
as indicated by the strain at the time of crack generation of 30%
or more. In the same manner as the tube sheets of Comparative
Examples 8, 9 and 11, the tube sheets (A) to (I) of Examples 12 to
20 had excellent mechanical properties as indicated by the strain
at the time of crack generation of 24% or more, indicating their
excellent mechanical properties. On the other hand, the tube sheet
(L) of Comparative Example 10 had a strain at the time of crack
generation of 17%, indicating its poor mechanical properties.
[0643] In the same manner as the tube sheets of (J), (L), and (M)
of Comparative Examples 8, 10 and 11, the tube sheets (A) to (I) of
Examples 12 to 20 had excellent oil resistance as indicated by the
change in the haze value due to the application of salad oil. On
the other hand, the tube sheet (K) of Comparative Example 9 showed
a significant change of the haze value due to salad oil
application, indicating its poor oil resistance.
[0644] Since the tube sheets of Examples 12 to 20 have excellent
steam barrier properties, mechanical characteristics, oil
resistance, pliability, and moldability, and particularly superior
steam barrier properties at a high temperature, the tube sheets are
preferable as a packing material of an infusion solution bag.
Pellet Production Example 1
[0645] 0.1 part by weight of an antioxidant
(tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]metha-
ne (Irganox 1010 manufactured by Ciba Geigy), hereinafter referred
to as "Antioxidant A") was added to 100 parts by weight of the
hydrogenated ring-open polymer (1) and the mixture was kneaded
using a twin-screw kneader (TEM35B manufactured by Toshiba Machine
Co., Ltd.) to obtain pellets (A).
Pellet Production Example 2
[0646] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (11) obtained in
Example 6 and the mixture was kneaded using a twin-screw kneader
(TEM35B manufactured by Toshiba Machine Co., Ltd.) to obtain
pellets (B).
Pellet Production Example 3
[0647] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (12) obtained in
Example 7 and the mixture was kneaded using a twin-screw kneader
(TEM35B manufactured by Toshiba Machine Co., Ltd.) to obtain
pellets (C).
Pellet Production Example 4
[0648] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (14) obtained in
Example 9 and the mixture was kneaded using a twin-screw kneader
(TEM35B manufactured by Toshiba Machine Co., Ltd.) to obtain
pellets (D).
Pellet Production Example 5
[0649] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (13) obtained in
Example 8 and the mixture was kneaded using a twin-screw kneader to
obtain pellets (E).
Pellet Production Example 6
[0650] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (15) obtained in
Example 10 and the mixture was kneaded using a twin-screw kneader
(TEM35B manufactured by Toshiba Machine Co., Ltd.) to obtain
pellets (F).
Pellet Production Example 7
[0651] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (8) obtained in
Reference Example 1 and the mixture was kneaded using a twin-screw
kneader (TEM35B manufactured by Toshiba Machine Co., Ltd.) to
obtain pellets (G).
Pellet Production Example 8
Ring-Opening Polymerization and Hydrogenation Reaction
[0652] Polymerization was carried out in the same manner as in
Pellet Production Example 1, except that 200 parts by weight of
methyltetracyclododecene (MTD) and 50 parts by weight of
dicyclopentadiene were used instead of 2-norbornene, and the amount
of 1-hexene used was 0.40 parts by weight. The polymerization
conversion rate was about 100%. The weight average molecular weight
(Mw) of the resulting ring-open polymer (17) was 56,000, and the
molecular weight distribution (Mw/Mn) was 2.0. The hydrogenation
reaction was carried out in the same manner as in Pellet Production
Example 3 to obtain a hydrogenated ring-open polymer (19).
(Properties of Polymer)
[0653] The degree of hydrogenation of the resulting hydrogenated
ring-open polymer (19) was 99.9%, the weight average molecular
weight (Mw) was 55,000, the molecular weight distribution (Mw/Mn)
was 3.1, the glass transition temperature was 140.degree. C., and a
melting point was not observed.
(Preparation of Resin Composition)
[0654] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (19) and the
mixture was kneaded using a twin-screw kneader (TEM35B manufactured
by Toshiba Machine Co., Ltd.) to obtain pellets (H).
Pellet Production Example 9
Ring-Opening Polymerization and Hydrogenation Reaction
[0655] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (18) obtained in
Comparative Example 6 and the mixture was kneaded using a
twin-screw kneader (TEM35B manufactured by Toshiba Machine Co.,
Ltd.) to obtain pellets (I).
Pellet Production Example 10
[0656] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (7) obtained in
Comparative Example 2 and the mixture was kneaded using a
twin-screw kneader (TEM35B manufactured by Toshiba Machine Co.,
Ltd.) to obtain pellets (J).
Example 21
Sheet Forming
[0657] The pellets (A) were molded into a monolayer sheet (A)
(thickness: 250 .mu.m) by T-die molding using a hanger manifold
T-die film melt extruding press machine (stationary type
manufactured by GSI Creos Corp.) equipped with a screw having a
screw diameter of 20 mm, a compression ratio of 3.1, and L/D=30
under the following conditions.
[0658] The type, composition, Mw, Mw/Mn, hydrogenation degree (%),
isomerization ratio (%), and melting point (.degree. C.) of the
hydrogenated ring-open polymer forming the monolayer sheet (A) are
shown in Table 7.
<Molding Conditions>
Die lip: 0.8 mm
[0659] Molten resin temperature: 180.degree. C.
Width of T-die: 300 mm
[0660] Cooling roller: 120.degree. C. Casting roll: 130.degree.
C.
[0661] The monolayer sheet (A) obtained above was molded by blister
molding at 130.degree. C. using a medication packing machine
(FBP-M2 manufactured by CKD) to obtain a process sheet (1) having
10 cylindrical portions (pockets: diameter 9 mm.times.height 5 mm)
arranged five lengthwise and two horizontally at center intervals
of 15 mm, for enclosing tablets (8 mm .phi..times.maximum thickness
of 4 mm) on the monolayer film (A).
[0662] The oil resistance of the resulting process sheet (1) was
evaluated. The results are shown in Table 8.
[0663] Without filling the medication, the plane on the concave
side (unprojected side) of the pocket of the process sheet (1) was
layered with the adhesive plane of an aluminum foil for PTP
(manufactured by Nippon Foil Mfg. Co., Ltd.) (thickness 20 .mu.m).
After heat-sealing at 210.degree. C. and inserting a slitter at
175.degree. C., the layered material was punched to obtain a PTP
(1) with a width of 37 mm, a length of 94 mm, and a corner of 5
mmR, having a total of ten pockets (five lengthwise and two
horizontally). The blister moldability of the pockets of the
resulting PTP (1) was evaluated. The results are shown in Table
8.
[0664] Table 8 also shows the steam barrier properties of the
monolayer sheet (A).
Example 22
Sheet Forming
[0665] The pellets (B) were molded into a monolayer sheet (B)
(thickness: 250 .mu.m) by T-die molding using a hanger manifold
T-die film melt extruding press machine (stationary type
manufactured by GSI Creos Corp.) equipped with a screw having a
screw diameter of 20 mm, a compression ratio of 3.1, and L/D=30
under the following conditions.
[0666] The type, composition, Mw, Mw/Mn, hydrogenation degree (%),
isomerization ratio (%), and melting point (.degree. C.) of the
hydrogenated ring-open polymer forming the monolayer sheet (B) are
shown in Table 7.
<Molding Conditions>
Die lip: 0.8 mm
[0667] Molten resin temperature: 180.degree. C.
Width of T-die: 300 mm
[0668] Cooling roller: 120.degree. C. Casting roll: 130.degree.
C.
[0669] A process sheet (2) and a PTP (2) were prepared in the same
manner as in Example 21, except for using the monolayer sheet (B)
instead of the monolayer sheet (A). Steam barrier properties of the
monolayer sheet (B), oil resistance of the resulting process sheet
(2), and the blister moldability of the pockets of the PTP (2) were
evaluated. The measurement results are shown in Table 8.
[0670] Table 8 also shows the steam barrier properties of the
monolayer sheet (B).
Example 23
Sheet Forming
[0671] The pellets (C) were molded into a monolayer sheet (C1)
(thickness: 250 .mu.m), a monolayer sheet (C2) (thickness: 215
.mu.m), and a monolayer sheet (C3) (thickness: 180 .mu.m) by T-die
molding using a hanger manifold T-die film melt extruding press
machine (stationary type manufactured by GSI Creos Corp.) equipped
with a screw having a screw diameter of 20 mm, a compression ratio
of 3.1, and L/D=30 under the following conditions.
[0672] The type, composition, Mw, Mw/Mn, hydrogenation degree (%),
isomerization ratio (%), and melting point (.degree. C.) of the
hydrogenated ring-open polymer forming the monolayer sheet (C1) are
shown in Table 7.
<Molding Conditions>
Die lip: 0.8 mm
[0673] Molten resin temperature: 180.degree. C.
Width of T-die: 300 mm
[0674] Cooling roller: 120.degree. C. Casting roll: 130.degree.
C.
[0675] A process sheet (3) was prepared in the same manner as in
Example 21, except that the monolayer sheet (C1) was used instead
of the monolayer sheet (A) and the blister molding temperature was
120.degree. C. The resulting process sheet (3) was molded in the
same manner as in Example 21 to obtain a PTP (3). Oil resistance of
the resulting PTP (3) and blister moldability of the pockets of the
PTP (3) were evaluated. The results are shown in Table 8.
[0676] Table 8 also shows the steam barrier properties of the
monolayer sheet (C1).
Example 24
Sheet Forming
[0677] The pellets (D) were molded into a monolayer sheet (D)
(thickness: 250 .mu.m) by T-die molding using a hanger manifold
T-die film melt extruding press machine (stationary type
manufactured by GSI Creos Corp.) equipped with a screw having a
screw diameter of 20 mm, a compression ratio of 3.1, and L/D=30
under the following conditions.
[0678] The type, composition, Mw, Mw/Mn, hydrogenation degree (%),
isomerization ratio (%), and melting point (.degree. C.) of the
hydrogenated ring-open polymer forming the monolayer sheet (D) are
shown in Table 7.
<Molding Conditions>
Die lip: 0.8 mm
[0679] Molten resin temperature: 170.degree. C.
Width of T-die: 300 mm
[0680] Cooling roller: 100.degree. C. Casting roll: 110.degree.
C.
[0681] A process sheet (4) was prepared in the same manner as in
Example 21, except that the monolayer sheet (D) was used instead of
the monolayer sheet (A) and the blister molding temperature was
105.degree. C. The resulting process sheet (4) was molded in the
same manner as in Example 21 to obtain a PTP (4). Oil resistance of
the resulting PTP (4) and blister moldability of the pockets of the
PTP (4) were evaluated. The results are shown in Table 8.
[0682] Table 8 also shows the steam barrier properties of the
monolayer sheet (D).
Example 25
Sheet Forming
[0683] The pellets (E) were molded into a monolayer sheet (E)
(thickness: 250 .mu.m) by T-die molding using a hanger manifold
T-die film melt extruding press machine (stationary type
manufactured by GSI Creos Corp.) equipped with a screw having a
screw diameter of 20 mm, a compression ratio of 3.1, and L/D=30
under the following conditions.
[0684] The type, composition, Mw, Mw/Mn, hydrogenation degree (%),
isomerization ratio (%), and melting point (.degree. C.) of the
hydrogenated ring-open polymer forming the monolayer sheet (E) are
shown in Table 7.
<Molding Conditions>
Die lip: 0.8 mm
[0685] Molten resin temperature: 180.degree. C.
Width of T-die: 300 mm
[0686] Cooling roller: 120.degree. C. Casting roll: 130.degree.
C.
[0687] A process sheet (5) was prepared in the same manner as in
Example 21, except for using the monolayer sheet (E) instead of the
monolayer sheet (A). Steam barrier properties of the monolayer
sheet (E), oil resistance of the resulting process sheet (5) and
the PTP (5), and blister moldability of the pockets of the PTP (5)
were evaluated. The results are shown in Table 8.
[0688] Table 8 also shows the steam barrier properties of the
monolayer sheet (E).
Example 26
Sheet Forming
[0689] The pellets (F) were molded into a monolayer sheet (F)
(thickness: 250 .mu.m) by T-die molding using a hanger manifold
T-die film melt extruding press machine (stationary type
manufactured by GSI Creos Corp.) equipped with a screw having a
screw diameter of 20 mm, a compression ratio of 3.1, and L/D=30
under the following conditions.
[0690] The type, composition, Mw, Mw/Mn, hydrogenation degree (%),
isomerization ratio (%), and melting point (.degree. C.) of the
hydrogenated ring-open polymer forming the monolayer sheet (F) are
shown in Table 7.
<Molding Conditions>
Die lip: 0.8 mm
[0691] Molten resin temperature: 180.degree. C.
Width of T-die: 300 mm
[0692] Cooling roller: 120.degree. C. Casting roll: 130.degree.
C.
[0693] A process sheet (6) was prepared in the same manner as in
Example 21, except for using the monolayer sheet (F) instead of the
monolayer sheet (A). The resulting process sheet (6) was molded in
the same manner as in Example 21 to obtain a PTP (6). Steam barrier
properties of the monolayer sheet (F), oil resistance of the
resulting process sheet (6), and the blister processability of the
pockets of the PTP (6) were evaluated. The results are shown in
Table 8.
[0694] Table 8 also shows the steam barrier properties of the
monolayer sheet (F).
Example 27
Sheet Forming
[0695] The pellets (G) were molded into a monolayer sheet (G)
(thickness: 250 .mu.m) by T-die molding using a hanger manifold
T-die film melt extruding press machine (stationary type
manufactured by GSI Creos Corp.) equipped with a screw having a
screw diameter of 20 mm, a compression ratio of 3.1, and L/D=30
under the following conditions.
[0696] The type, composition, Mw, Mw/Mn, hydrogenation degree (%),
isomerization ratio (%), and melting point (.degree. C.) of the
hydrogenated ring-open polymer forming the monolayer sheet (G) are
shown in Table 7.
<Molding Conditions>
Die lip: 0.8 mm
[0697] Molten resin temperature: 180.degree. C.
Width of T-die: 300 mm
[0698] Cooling roller: 120.degree. C. Casting roll: 130.degree.
C.
[0699] A process sheet (7) and a PTP (7) were prepared in the same
manner as in Example 21, except for using the monolayer sheet (G)
instead of the monolayer sheet (A). Steam barrier properties of the
monolayer sheet (G) and blister processability of the pockets of
the resulting process sheet (7) and the PTP (7) were evaluated. The
results are shown in Table 8.
[0700] Table 8 also shows the steam barrier properties of the
monolayer sheet (G).
Example 28
[0701] A non-stretched polypropylene film (Pylene Film-CT,
manufactured by Toyobo Co., Ltd. thickness: 30 .mu.m) was attached
to one side of the monolayer film (C2) via a urethane adhesive at
70.degree. C. to obtain a multilayer film (1) (total thickness: 250
.mu.m).
[0702] A process sheet (8) was prepared in the same manner as in
Example 21, except for using the multilayer sheet (1) instead of
the monolayer sheet (A). The resulting process sheet (8) was molded
in the same manner as in Example 21 to obtain a PTP (8) with the
non-stretched polypropylene film layer being disposed on the convex
side of the PTP (8). Oil resistance of the resulting process sheet
(8) and blister moldability of the pockets of the PTP (8) were
evaluated. The results are shown in Table 9.
[0703] Table 9 also shows steam barrier properties of the
multilayer sheet (1).
Example 29
[0704] The pellets (C) and a linear low density polyethylene having
a melting point of 126.degree. C. and a density of 0.937 g/cm.sup.3
(UMERIT 4040F manufactured by Ube Industries, Ltd.) were molded
into a multilayer sheet consisting of the pellet (C) and the linear
low density polyethylene (thickness: pellet (C): 165 .mu.m, linear
low density polyethylene: 50 .mu.m, total: 215 .mu.m) by T-die
molding using a hanger manifold T-die film melt extruding press
machine (stationary type manufactured by GSI Creos Corp.) equipped
with a screw having a screw diameter of 20 mm, a compression ratio
of 3.1, and L/D=30 under the following conditions.
<Molding Conditions>
Die lip: 0.8 mm
[0705] (Pellet (C)) Molten resin temperature: 180.degree. C.
(Linear low density polyethylene) Molten resin temperature:
180.degree. C.
Width of T-die: 300 mm
[0706] Cooling roller: 110.degree. C. Casting roll: 120.degree.
C.
[0707] A non-stretched nylon film (Rayfan NO manufactured by Toyobo
Advanced Film Co., Ltd., thickness: 30 .mu.m) was attached to one
side of the resulting multilayer film of pellet (C) and the linear
low density polyethylene via a urethane adhesive at 70.degree. C.
to obtain a multilayer film (2) (total thickness: 250 .mu.m).
[0708] A process sheet (9) was prepared in the same manner as in
Example 21, except for using the multilayer sheet (2) instead of
the monolayer sheet (A). The resulting process sheet (9) was molded
in the same manner as in Example 21 to obtain a PTP (9) with the
non-stretched nylon film layer being disposed on the convex side of
the PTP (9). Oil resistance of the resulting process sheet (9) and
blister moldability of the pockets of the PTP (9) were evaluated.
The results are shown in Table 9.
[0709] Table 9 also shows steam barrier properties of the
multilayer sheet (2).
Example 30
[0710] A non-stretched polypropylene film (Pylene Film-CT,
manufactured by Toyobo Co., Ltd. thickness: 30 .mu.m) was attached
to both sides of the monolayer film (C3) via a urethane adhesive at
70.degree. C. to obtain a multilayer film (3) (total thickness: 250
.mu.m).
[0711] A process sheet (10) was prepared in the same manner as in
Example 21, except for using the multilayer sheet (3) instead of
the monolayer sheet (A). The resulting process sheet (10) was
molded in the same manner as in Example 21 to obtain a PTP (10).
Steam barrier properties of the multilayer sheet (3), oil
resistance of the resulting process sheet (10), and blister
moldability of the pockets of the PTP (10) were evaluated. The
results are shown in Table 9.
[0712] Table 9 also shows steam barrier properties of the
multilayer sheet (3).
Comparative Example 12
Sheet Forming
[0713] The pellets (H) were molded into a monolayer sheet (H1)
(thickness: 250 .mu.m) and a monolayer sheet (H2) (thickness: 180
.mu.m) by T-die molding using a hanger manifold T-die film melt
extruding press machine (stationary type manufactured by GSI Creos
Corp.) equipped with a screw having a screw diameter of 20 mm, a
compression ratio of 2.5, and L/D=30 under the following
conditions.
[0714] The type, composition, Mw, Mw/Mn, hydrogenation degree (%),
isomerization ratio (%), and melting point (.degree. C.) of the
hydrogenated ring-open polymer forming the monolayer sheet (H1) are
shown in Table 7.
<Molding Conditions>
Die lip: 0.8 mm
[0715] Molten resin temperature: 230.degree. C.
Width of T-die: 300 mm
[0716] Cooling roller: 85.degree. C. Casting roll: 95.degree.
C.
[0717] A process sheet (11) was prepared in the same manner as in
Example 21, except that the monolayer sheet (H1) was used instead
of the monolayer sheet (A) and the blister molding temperature was
110.degree. C. The resulting process sheet (11) was molded in the
same manner as in Example 21 to obtain a PTP (11). Oil resistance
of the resulting PTP (11) and blister moldability of the pockets of
the PTP (11) were evaluated. The results are shown in Table 8.
[0718] Table 8 also shows steam barrier properties of the monolayer
sheet (H1).
Comparative Example 13
Sheet Forming
[0719] The pellets (I) were molded into a monolayer sheet (I)
(thickness: 250 .mu.m) by T-die molding using a hanger manifold
T-die film melt extruding press machine (stationary type
manufactured by GSI Creos Corp.) equipped with a screw having a
screw diameter of 20 mm, a compression ratio of 3.1, and L/D=30
under the following conditions.
[0720] The type, composition, Mw, Mw/Mn, hydrogenation degree (%),
isomerization ratio (%), and melting point (.degree. C.) of the
hydrogenated ring-open polymer forming the monolayer sheet (I) are
shown in Table 7.
<Molding Conditions>
Die lip: 0.8 mm
[0721] Molten resin temperature: 150.degree. C.
Width of T-die: 300 mm
[0722] Cooling roller: 80.degree. C. Casting roll: 90.degree.
C.
[0723] A process sheet (12) was prepared in the same manner as in
Example 21, except that the monolayer sheet (I) was used instead of
the monolayer sheet (A) and the blister molding temperature was
95.degree. C. The resulting process sheet (12) was molded in the
same manner as in Example 21 to obtain a PTP (12).
[0724] Oil resistance of the resulting process sheet (12) and
blister moldability of the pockets of the PTP (12) were evaluated.
The results are shown in Table 8.
[0725] Table 8 also shows steam barrier properties of the monolayer
sheet (I).
Comparative Example 14
Sheet Forming
[0726] The pellets (J) were molded into a monolayer sheet (J)
(thickness: 250 .mu.m) by T-die molding using a hanger manifold
T-die film melt extruding press machine (stationary type
manufactured by GSI Creos Corp.) equipped with a screw having a
screw diameter of 20 mm, a compression ratio of 3.1, and L/D=30
under the following conditions.
[0727] The type, composition, Mw, Mw/Mn, hydrogenation degree (%),
isomerization ratio (%), and melting point (.degree. C.) of the
hydrogenated ring-open polymer forming the monolayer sheet (J) are
shown in Table 7.
<Molding Conditions>
Die lip: 0.8 mm
[0728] Molten resin temperature: 310.degree. C.
Width of T-die: 300 mm
[0729] Cooling roller: 220.degree. C. Casting roll: 230.degree.
C.
[0730] The experiment of preparing a process sheet was carried out
in the same manner as in Example 21, except that the monolayer
sheet (J) was used instead of the monolayer sheet (A) and the
blister molding temperature of 260.degree. C., which is around the
upper limit of the molding machine, was employed. The pocket
portions were not dented, failing to produce a process sheet.
[0731] Table 8 shows steam barrier properties of the monolayer
sheet (J).
Comparative Example 15
[0732] A multilayer sheet (4), a process sheet (13) and a PTP (13)
were prepared in the same manner as in Example 21, except for using
the monolayer sheet (H2) instead of the monolayer sheet (A).
[0733] Oil resistance of the resulting process sheet (13) and
blister moldability of the pockets of the PTP (13) were evaluated.
The results are shown in Table 9.
[0734] Table 9 also shows steam barrier properties of the
multilayer sheet (4).
TABLE-US-00007 TABLE 7 Hydrogenated ring-open polymer Monolayer
Hydrogenation Isomerization Melting sheet No. Composition Mw Mw/Mn
rate (%) degree (%) point (.degree. C.) Example 21 A 1 NB 100 82200
2.9 99.9 5 140 22 B 11 NB/MNB = 98/2 100000 2.9 99.9 8 136 23 C1 12
NB/MNB = 96/4 80000 2.9 99.9 8 133 24 D 14 NB/MNB = 91/9 98800 3.8
99.9 7 114 25 E 13 NB/DCP = 99/1 160000 1.8 99.9 0 139 26 F 15
NB/DCP = 96/4 81300 3.8 99.9 9 134 27 G 8 NB 100 64200 1.3 99.75 0
143 Comparative 12 H1 19 DCP 100 53000 3.6 99.9 -- -- Example 13 I
17 NB/TCD = 89/11 315000 4.9 99.0 9 100 14 J 7 DCP 100 -- -- -- --
273
TABLE-US-00008 TABLE 8 Steam barrier properties of Oil resistance
Blister moldability Monolayer monolayer sheet (g/m.sup.2 24 h)) of
process (number of crushed sheet 40.degree. C. .times. 90% RH
50.degree. C. .times. 90% RH Process sheet sheet PTP pockets)
Example 21 A 0.07 0.21 1 After 6 days 1 5 22 B 0.12 0.25 2 After 6
days 2 1 23 C1 0.15 0.28 3 After 5 days 3 0 24 D 0.21 0.36 4 After
5 days 4 0 25 E 0.11 0.26 5 After 8 days 5 4 26 F 0.17 0.30 6 After
4 days 6 0 27 G 0.09 0.23 7 After 4 days 7 10 Comparative 12 H1
0.43 0.80 11 Within 1 hour 11 3 Example 13 I 0.31 0.64 12 After 7
days 12 83 14 J 0.40 0.70 -- -- -- --
TABLE-US-00009 TABLE 9 Blister Steam barrier properties of
moldability Multilayer Layer multilayer sheet (g/(m.sup.2 24 h))
Process Oil resistance of (number of sheet constitution 40.degree.
C. .times. 90% RH 50.degree. C. .times. 90% RH sheet process sheet
PTP crushed pockets) Example 28 1 C2/PP 0.07 0.21 8 No change for 8
0 10 days or more 29 2 Ny/C/PE 0.12 0.25 9 No change for 9 0 10
days or more 30 3 PP/C3/PP 0.15 0.28 10 No change for 10 0 10 days
or more Comparative 15 4 PP/H2/PP 0.45 1.00 13 No change for 13 2
Example 10 days or more PP = Polypropylene, PE = Polyethylene, Ny =
Nylon
[0735] As can be seen from Tables 8 and 9, the blister molded
sheets of Examples 21 to 27 and Examples 28 to 30 (monolayer sheets
(A) to (G) and multilayer sheets (1) to (3)) had a moisture
permeability of 0.21 g/(m.sup.224 h) or less at 40.degree. C. and
90% RH, and 0.36 g/(m.sup.224 h) or less at 50.degree. C. and 90%
RH, showing excellent steam barrier properties, particularly at a
high temperature. On the other hand, the blister molded sheets of
Comparative Examples 12 to 15 (monolayer sheets (H1) to (J) and
multilayer sheet (4)) had a moisture permeability of 0.31 to 0.45
g/(m.sup.224 h) at 40.degree. C. and 90% RH, and 0.64 to 1.0
g/(m.sup.224 h) at 50.degree. C. and 90% RH, showing inferior steam
barrier properties, particularly at a high temperature.
[0736] The number of crushed pockets in the PTPs (1) to (10) of
Examples 21 to 27 and Examples 28 to 30 and PTPs (11) and (13) of
Comparative Examples 12 and 15 was 10 out of 100 pockets, showing
excellent blister moldability. On the other hand, in the PTP (12)
of Comparative Example 13, 83 pockets out of 100 pockets were
crushed, indicating poor blister moldability.
[0737] The process sheets (1) to (10) of Examples 21 to 27 and
Examples 28 to 30 and the process sheets (12) of Comparative
Example 2 required four days or more before being whitened, showing
excellent oil resistance. On the other hand, the process sheet (11)
of Comparative Example 12 was whitened within one hour in the oil
resistance evaluation test, indicating poor oil resistance.
[0738] The monolayer sheet (J) had too high a melting point to be
blister molded.
[0739] Based on the above results, the blister molding sheet and
the blister-molded article of the present invention were confirmed
to have excellent steam barrier properties particularly at a high
temperature, superior blister moldability, and good oil
resistance.
Film Production Example 1
[0740] The pellets (A) obtained in Pellet Production Example 1 were
molded into a monolayer film (A) (thickness: 30 .mu.m) by T-die
molding using a hanger manifold T-die film melt extruding press
machine (stationary type manufactured by GSI Creos Corp.) equipped
with a screw having a screw diameter of 20 mm, a compression ratio
of 3.1, and L/D=30 under the following conditions.
<Molding Conditions>
Die lip: 0.8 mm
[0741] Molten resin temperature: 180.degree. C.
Width of T-die: 300 mm
[0742] Cooling roller: 120.degree. C. Casting roll: 130.degree.
C.
Film Production Example 2
[0743] The pellets (B) obtained in Pellet Production Example 2 were
molded into a monolayer film (B) (thickness: 30 .mu.m) by T-die
molding using a hanger manifold T-die film melt extruding press
machine (stationary type manufactured by GSI Creos Corp.) equipped
with a screw having a screw diameter of 20 mm, a compression ratio
of 3.1, and L/D=30 under the following conditions.
<Molding Conditions>
Die lip: 0.8 mm
[0744] Molten resin temperature: 180.degree. C.
Width of T-die: 300 mm
[0745] Cooling roller: 120.degree. C. Casting roll: 130.degree.
C.
Film Production Example 3
[0746] The pellets (C) obtained in Pellet Production Example 3 were
molded into a monolayer film (C) (thickness: 30 .mu.m) by T-die
molding using a hanger manifold T-die film melt extruding press
machine (stationary type manufactured by GSI Creos Corp.) equipped
with a screw having a screw diameter of 20 mm, a compression ratio
of 3.1, and L/D=30 under the following conditions.
<Molding Conditions>
Die lip: 0.8 mm
[0747] Molten resin temperature: 180.degree. C.
Width of T-die: 300 mm
[0748] Cooling roller: 120.degree. C. Casting roll: 130.degree.
C.
Film Production Example 4
[0749] The pellets (D) obtained in Pellet Production Example 4 were
molded into a monolayer film (D) (thickness: 30 .mu.m) by T-die
molding using a hanger manifold T-die film melt extruding press
machine (stationary type manufactured by GSI Creos Corp.) equipped
with a screw having a screw diameter of 20 mm, a compression ratio
of 3.1, and L/D=30 under the following conditions.
<Molding Conditions>
Die lip: 0.8 mm
[0750] Molten resin temperature: 170.degree. C.
Width of T-die: 300 mm
[0751] Cooling roller: 100.degree. C. Casting roll: 110.degree.
C.
Film Production Example 5
[0752] The pellets (E) obtained in Pellet Production Example 5 were
molded into a monolayer film (E) (thickness: 30 .mu.m) by T-die
molding using a hanger manifold T-die film melt extruding press
machine (stationary type manufactured by GSI Creos Corp.) equipped
with a screw having a screw diameter of 20 mm, a compression ratio
of 3.1, and L/D=30 under the following conditions.
<Molding Conditions>
Die lip: 0.8 mm
[0753] Molten resin temperature: 180.degree. C.
Width of T-die: 300 mm
[0754] Cooling roller: 120.degree. C. Casting roll: 130.degree.
C.
Film Production Example 6
[0755] The pellets (F) obtained in Pellet Production Example 6 were
molded into a monolayer film (F) (thickness: 30 .mu.m) by T-die
molding using a hanger manifold T-die film melt extruding press
machine (stationary type manufactured by GSI Creos Corp.) equipped
with a screw having a screw diameter of 20 mm, a compression ratio
of 3.1, and L/D=30 under the following conditions.
<Molding Conditions>
Die lip: 0.8 mm
[0756] Molten resin temperature: 180.degree. C.
Width of T-die: 300 mm
[0757] Cooling roller: 120.degree. C. Casting roll: 130.degree.
C.
Film Production Example 7
[0758] The pellets (G) obtained in Pellet Production Example 7 were
molded into a monolayer film (G1) (thickness: 30 .mu.m) and a
monolayer film (G2) (thickness: 50 .mu.m) by T-die molding using a
hanger manifold T-die film melt extruding press machine (stationary
type manufactured by GSI Creos Corp.) equipped with a screw having
a screw diameter of 20 mm, a compression ratio of 3.1, and L/D=30
under the following conditions.
<Molding Conditions>
Die lip: 0.8 mm
[0759] Molten resin temperature: 180.degree. C.
Width of T-die: 300 mm
[0760] Cooling roller: 120.degree. C. Casting roll: 130.degree.
C.
Film Production Example 8
[0761] 0.1 part by weight of Antioxidant A was added to 100 parts
by weight of the hydrogenated ring-open polymer (9) obtained in
Comparative Example 3 and the mixture was kneaded using a
twin-screw kneader (TEM35B manufactured by Toshiba Machine Co.,
Ltd.) to obtain pellets (K).
(Film Forming)
[0762] The pellets (K) were molded into a monolayer film (H)
(thickness: 30 .mu.m) by T-die molding using a hanger manifold
T-die film melt extruding press machine (stationary type
manufactured by GSI Creos Corp.) equipped with a screw having a
screw diameter of 20 mm, a compression ratio of 2.5, and L/D=30
under the following conditions.
<Molding Conditions>
Die lip: 0.8 mm
[0763] Molten resin temperature: 250.degree. C.
Width of T-die: 300 mm
[0764] Cooling roller: 125.degree. C. Casting roll: 135.degree.
C.
Film Production Example 9
[0765] The pellets (I) obtained in Pellet Production Example 9 were
molded into a monolayer film (I) (thickness: 30 .mu.m) by T-die
molding using a hanger manifold T-die film melt extruding press
machine (stationary type manufactured by GSI Creos Corp.) equipped
with a screw having a screw diameter of 20 mm, a compression ratio
of 3.1, and L/D=30 under the following conditions.
<Molding Conditions>
Die lip: 0.8 mm
[0766] Molten resin temperature: 150.degree. C.
Width of T-die: 300 mm
[0767] Cooling roller: 80.degree. C. Casting roll: 90.degree.
C.
Film Production Example 10
[0768] The pellets (J) obtained in Pellet Production Example 10
were molded into a monolayer film (J) (thickness: 30 .mu.m) by
T-die molding using a hanger manifold T-die film melt extruding
press machine (stationary type manufactured by GSI Creos Corp.)
equipped with a screw having a screw diameter of 20 mm, a
compression ratio of 3.1, and L/D=30 under the following
conditions. A high temperature was necessary for molding the
pellets (J), and coloration due to resin burning was observed on
the resulting monolayer film.
<Molding Conditions>
Die lip: 0.8 mm
[0769] Molten resin temperature: 310.degree. C.
Width of T-die: 300 mm
[0770] Cooling roller: 220.degree. C. Casting roll: 230.degree.
C.
[0771] The weight average molecular weight, molecular weight
distribution, melting point, and isomerization ratio of the
monolayer films (A) to (J) obtained in Film Production Examples 1
to 10 are shown in Table 10.
TABLE-US-00010 TABLE 10 Hydrogenated ring-open polymer Monolayer
Hydrogenation Isomerization Melting film No. Composition Mw Mw/Mn
rate (%) degree (%) point (.degree. C.) Film 1 A 1 NB 100 82200 2.9
99.9 5 140 Production 2 B 11 NB/MNB = 98/2 100000 2.9 99.9 8 136
Example 3 C 12 NB/MNB = 96/4 80000 2.9 99.9 8 133 4 D 14 NB/MNB =
91/9 98800 3.8 99.9 7 114 5 F 13 NB/DCP = 99/1 160000 1.8 99.9 0
139 6 E 15 NB/DCP = 96/4 81300 3.8 99.9 9 134 7 G 8 NB 100 64200
1.3 99.75 0 143 8 H 9 MTD/DCP = 80/20 55000 3.1 99.9 -- -- 9 I 18
NB/TCD = 89/11 315000 4.9 99.0 9 100 10 J 7 DCP 100 -- -- -- --
273
Example 31
[0772] The monolayer film (A) was attached to one side of an
ethylene-vinyl alcohol copolymer film with an ethylene content of
32% (Eval F manufactured by Kuraray Co., Ltd. thickness: 15 .mu.m)
via a urethane adhesive (Takenate/Takelac manufactured by Mitsui
Takeda Chemical Co., Ltd.) at 70.degree. C. to obtain a multilayer
film (1) (total thickness: 50 .mu.m). The steam barrier properties
and oil resistance of the resulting multilayer film (1) were
evaluated. The results are shown in Table 11.
[0773] The resulting multilayer film (1) was cut into 20 cm
squares. Two sheets of the square cut film were layered with the
ethylene-vinyl alcohol copolymer film layers being face to face,
and three sides were heat-sealed with a hot melt adhesive (Aron
Melt PPET manufactured by Toagosei Co., Ltd) at 190.degree. C. and
0.2 MPa for two seconds using a heat-sealing tester (TP-701-B
manufactured by Tester Industrial Co, Ltd.) to obtain a bag
(1).
[0774] The bag (1) was filled with 70 ml of 5% brine and the open
side was heat-sealed in the same manner as above to obtain a brine
pack (1). The brine pack (1) had no defects such as breaking,
cracks, inadequate sealing, and the like. Impact resistance of the
brine pack (1) was evaluated. The results are shown in Table
11.
Example 32
[0775] A multilayer film (2), a bag (2), and a brine pack (2) were
prepared in the same manner as in Example 31, except for using the
monolayer film (B) instead of the monolayer film (A). The brine
pack (2) had no defects such as breaking, cracks, inadequate
sealing, and the like.
[0776] Steam barrier properties and oil resistance of the resulting
multilayer film (2) and impact resistance of the brine pack (2)
were evaluated. The results are shown in Table 11.
Example 33
[0777] A multilayer film (3), a bag (3), and a brine pack (3) were
prepared in the same manner as in Example 31, except for using the
monolayer film (C) instead of the monolayer film (A). The brine
pack (3) had no defects such as breaking, cracks, inadequate
sealing, and the like.
[0778] Steam barrier properties and oil resistance of the resulting
multilayer film (3) and impact resistance of the brine pack (3)
were evaluated. The results are shown in Table 11.
Example 34
[0779] A multilayer film (4), a bag (4), and a brine pack (4) were
prepared in the same manner as in Example 31, except for using the
monolayer film (D) instead of the monolayer film (A). The brine
pack (4) had no defects such as breaking, cracks, inadequate
sealing, and the like.
[0780] Steam barrier properties and oil resistance of the resulting
multilayer film (4) and impact resistance of the brine pack (4)
were evaluated. The results are shown in Table 11.
Example 35
[0781] A multilayer film (5), a bag (5), and a brine pack (5) were
prepared in the same manner as in Example 35, except for using the
monolayer film (E) instead of the monolayer film (A). The brine
pack (5) had no defects such as breaking, cracks, inadequate
sealing, and the like.
[0782] Steam barrier properties and oil resistance of the resulting
multilayer film (5) and impact resistance of the brine pack (5)
were evaluated. The results are shown in Table 11.
Example 36
[0783] A multilayer film (6), a bag (6), and a brine pack (6) were
prepared in the same manner as in Example 31, except for using the
monolayer film (F) instead of the monolayer film (A). The brine
pack (6) had no defects such as breaking, cracks, inadequate
sealing, and the like.
[0784] Steam barrier properties and oil resistance of the resulting
multilayer film (6) and impact resistance of the brine pack (6)
were evaluated. The results are shown in Table 11.
Example 37
[0785] The pellets (C) and a linear low density polyethylene
(UMERIT 4040F manufactured by Ube Industries, Ltd.) were molded
into a multilayer film (7), consisting of the pellet (C) and the
linear low density polyethylene (thickness: pellet (C): 30 .mu.m,
linear low density polyethylene: 20 .mu.m, total: 50 .mu.m) by
T-die molding using a hanger manifold T-die film melt extruding
press machine (stationary type manufactured by GSI Creos Corp.)
equipped with a screw having a screw diameter of 20 mm, a
compression ratio of 3.1, and L/D=30 under the following
conditions.
<Molding Conditions>
Die lip: 0.8 mm
[0786] (Pellet (C)) Molten resin temperature: 180.degree. C.
(Linear low density polyethylene) Molten resin temperature:
180.degree. C.
Width of T-die: 300 mm
[0787] Cooling roller: 110.degree. C. Casting roll: 120.degree.
C.
[0788] The steam barrier properties and oil resistance of the
resulting multilayer film (7) were evaluated. The results are shown
in Table 11.
[0789] The resulting multilayer film (7) was cut into 20 cm
squares. Two sheets of the square cut film were layered with the
linear low density polyethylene layers being face to face, and
three sides were heat-sealed at 190.degree. C. and 0.2 MPa for two
seconds using a heat-sealing tester (TP-701-B manufactured by
Tester Industrial Co, Ltd.) to obtain a bag (7).
[0790] The bag (7) was filled with 70 ml of 5% brine and the open
side was heat-sealed in the same manner as above to obtain a brine
pack (7). The brine pack (7) had no defects such as breaking,
cracks, inadequate sealing, and the like. Impact resistance of the
brine pack (7) was evaluated. The results are shown in Table
11.
Example 38
[0791] A biaxial stretched nylon film (Harden Film manufactured by
Toyobo Co., Ltd. thickness: 15 .mu.m) was attached to one side of
the monolayer film (C) obtained above via a urethane adhesive
(Takenate/Takelac manufactured by Mitsui Takeda Chemical Co., Ltd.)
at 70.degree. C. to obtain a multilayer film (8) (total thickness:
50 .mu.m). The steam barrier properties and oil resistance of the
resulting multilayer film (8) were evaluated. The results are shown
in Table 11.
[0792] The resulting multilayer film (8) was cut into 20 cm
squares. Two sheets of the square cut film were layered with the
layers of pellets (C) being face to face, and three sides were
heat-sealed at 190.degree. C. and 0.2 MPa for two seconds using a
heat-sealing tester (TP-701-B manufactured by Tester Industrial Co,
Ltd.) to obtain a bag (8).
[0793] The bag (8) was filled with 70 ml of 5% brine and the open
side was heat-sealed in the same manner as above to obtain a brine
pack (8). The brine pack (8) had no defects such as breaking,
cracks, inadequate sealing, and the like. Impact resistance of the
brine pack (8) was evaluated. The results are shown in Table
11.
Example 39
[0794] A multilayer film (9), a bag (9), and a brine pack (9) were
prepared in the same manner as in Example 38, except for using the
monolayer film (G1) instead of the monolayer film (C). The brine
pack (9) had no defects such as breaking, cracks, inadequate
sealing, and the like.
[0795] Steam barrier properties and oil resistance of the resulting
multilayer film (9) and impact resistance of the brine pack (9)
were evaluated. The results are shown in Table 11.
Comparative Example 16
[0796] A multilayer film (10), a bag (10), and a brine pack (10)
were prepared in the same manner as in Example 31, except for using
the monolayer film (H) instead of the monolayer film (A). The brine
pack (10) had no defects such as breaking, cracks, inadequate
sealing, and the like.
[0797] Steam barrier properties and oil resistance of the resulting
multilayer film (10) and impact resistance of the brine pack (10)
were evaluated. The results are shown in Table 11.
Comparative Example 17
[0798] A multilayer film (11), a bag (11), and a brine pack (11)
were prepared in the same manner as in Example 31, except for using
the monolayer film (I) instead of the monolayer film (A). The brine
pack (11) had no defects such as breaking, cracks, inadequate
sealing, and the like.
[0799] Steam barrier properties and oil resistance of the resulting
multilayer film (11) and impact resistance of the brine pack (12)
were evaluated. The results are shown in Table 11.
Comparative Example 18
[0800] A multilayer film (12) was prepared in the same manner as in
Example 31, except for using the monolayer film (J) instead of the
monolayer film (A). A bag (12) and a brine pack (12) were also
obtained. The brine pack (12) had no defects such as breaking,
cracks, inadequate sealing, and the like.
[0801] The steam barrier properties and oil resistance of the
resulting multilayer film (12) were evaluated. The results are
shown in Table 11.
Comparative Example 19
[0802] A bag (13) and a brine pack (13) were prepared in the same
manner as in Example 31, except for using the monolayer film (G2)
instead of the multilayer film (1). The brine pack (13) had no
defects such as breaking, cracks, inadequate sealing, and the
like.
[0803] Steam barrier properties and oil resistance of the resulting
monolayer film (G2) and impact resistance of the brine pack (13)
were evaluated. The results are shown in Table 11.
[0804] Symbols shown in Table 11 have the following meanings.
EV: Ethylene-vinyl alcohol copolymer film layer AD: Urethane
adhesive layer A to F, G1, G2, and H to K: Hydrogenated norbornene
ring-open polymer layer LPE: Linear low density polyethylene layer
NY: Biaxial stretched nylon film layer
TABLE-US-00011 TABLE 11 Steam barrier Impact Layer properties
resistance of Film constitution (g/(m.sup.2 24 h) Brine bag brine
bag Oil resistance Example 31 Multilayer film (1) EV/AD/A 1.7 1 11
Whitened after 6 days 32 Multilayer film (2) EV/AD/B 1.8 2 4
Whitened after 6 days 33 Multilayer film (3) EV/AD/C 1.8 3 1
Whitened after 5 days 34 Multilayer film (4) EV/AD/D 2.5 4 0
Whitened after 5 days 35 Multilayer film (5) EV/AD/E 1.7 5 6
Whitened after 8 days 36 Multilayer film (6) EV/AD/F 2 6 2 Whitened
after 4 days 37 Multilayer film (7) C/LPE 1.9 7 1 Whitened after 5
days 38 Multilayer film (8) NY/AD/C 2 8 0 Whitened after 5 days 39
Multilayer film (9) NY/AD/G1 1.7 9 10 Whitened after 4 days
Comparative 16 Multilayer film (10) EV/AD/H 5 10 58 Whitened within
one hour Example 17 Multilayer film (11) EV/AD/I 4.1 11 46 Whitened
after 7 days 18 Multilayer film (12) EV/AD/J 3.3 12 72 Whitened
after 8 days 19 Monolayer film (G2) G2 1.1 13 97 Whitened after 4
days
[0805] As shown in Table 11, the multilayer films (multilayer
articles) of Examples 31 to 39 and the monolayer film of
Comparative Example 19 showed excellent steam barrier properties.
On the other hand, the multilayer films of Comparative Examples 16
to 18 exhibited poor steam barrier properties.
[0806] The multilayer films of Examples 31 to 39, the multilayer
films of Comparative Examples 17 and 18, and the monolayer film of
Comparative Example 19 exhibited excellent oil resistance. On the
other hand, the multilayer film of Comparative Example 16 exhibited
poor oil resistance.
[0807] Furthermore, the brine packs (packing material) of Examples
31 to 39 exhibited excellent impact resistance. On the other hand,
the brine pack of Comparative Examples 16 to 19 exhibited poor
impact resistance.
Example 40
[0808] The multilayer film (1) obtained above was cut into two A4
size sheets. Two sheets were layered with the ethylene-vinyl
alcohol copolymer film layers being face to face, and the four
sides were heat-sealed with a hot melt adhesive (Aron Melt PPET
manufactured by Toagosei Co., Ltd) at 190.degree. C. and 0.2 MPa
for two seconds using a heat-sealing tester (TP-701-B manufactured
by Tester Industrial Co, Ltd.) to obtain a bag. The bag was put
into and left in boiling water for 30 minutes and a 15 cm square in
the center was cut to obtain a boiled film (1).
[0809] Gas barrier properties of the multilayer film (1) and the
boiled film (1) were evaluated. The results are shown in Table
12.
Example 41
[0810] A boiled film (2) was obtained in the same manner as in
Example 40, except for using the multilayer film (3) instead of the
multilayer film (1).
[0811] Gas barrier properties of the multilayer film (3) and the
boiled film (2) were evaluated. The results are shown in Table
12.
Example 42
[0812] A boiled film (3) was obtained in the same manner as in
Example 40, except for using the multilayer film (6) instead of the
multilayer film (1).
[0813] Gas barrier properties of the multilayer film (6) and the
boiled film (3) were evaluated. The results are shown in Table
12.
Comparative Example 20
[0814] A boiled film (4) was obtained in the same manner as in
Example 40, except for using the multilayer film (10) instead of
the multilayer film (1).
[0815] Gas barrier properties of the multilayer film (10) and the
boiled film (4) were evaluated. The results are shown in Table
12.
Comparative Example 21
[0816] A boiled film (5) was obtained in the same manner as in
Example 40, except for using the multilayer film (11) instead of
the multilayer film (1).
[0817] Gas barrier properties of the multilayer film (11) and the
boiled film (5) were evaluated. The results are shown in Table
12.
Comparative Example 22
[0818] A multilayer film (13) and a boiled film (6) were obtained
in the same manner as in Example 40, except for using a biaxial
stretched polypropyrene film (Pylene Film OT manufactured by Toyobo
Co., Ltd. thickness: 30 .mu.m) instead of the multilayer film
(1).
[0819] Gas barrier properties of the resulting multilayer film (13)
and the boiled film (6) were evaluated. The results are shown in
Table 12.
TABLE-US-00012 TABLE 12 Multilayer Layer Gas barrier properties of
multilayer Gas barrier properties of boiled film film constitution
film (cm.sup.-3 m.sup.-2 day.sup.-1 atm.sup.-1) Boiled film
(cm.sup.-3m.sup.-2 day.sup.-1 atm.sup.-1) Example 40 1 EV/AD/A 0.32
1 0.39 41 3 EV/AD/C 0.33 2 0.41 42 6 EV/AD/F 0.35 3 0.42
Comparative 20 10 EV/AD/H 0.34 4 3.80 Example 21 11 EV/AD/J 0.34 5
3.10 22 13 EV/AD/PP 0.32 6 7.00
[0820] As shown in Table 12, the multilayer films having a gas
barrier resin layer of Examples 40 to 42 showed excellent gas
barrier properties both before and after the boiling treatment. On
the other hand, the multilayer films having a gas barrier resin
layer of Comparative Examples 20 to 22 showed excellent gas barrier
properties before the boiling treatment, but poor gas barrier
properties after the boiling treatment.
Example 43
[0821] 0.1 part by weight of an antioxidant
(tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]metha-
ne (Irganox 1010 manufactured by Ciba Geigy)) was added to 100
parts by weight of the hydrogenated ring-open polymer (1) obtained
in Example 1 and the mixture was kneaded using a twin-screw kneader
(TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain a
pelletized resin composition (A2).
(Fabrication of Blow-Molded Container)
[0822] A preform was prepared from the above pellets using a
stretching blow molding machine (manufactured by Nissei ASB Machine
Co., Ltd.) by injection molding at a cylinder temperature of
200.degree. C. and an injection mold die temperature of 60.degree.
C. Next, the preform was processed by blow molding at a preform
heating pot temperature of 100.degree. C., a blowing pressure of
0.5 MPa, and a blow die temperature of 60.degree. C. to obtain a
monolayer stretched blow-molded container (A3) with a lengthwise
stretching magnification y of 2.3 times, a horizontal stretching
magnification x of 2.1 times, and dimensions of 60 mm
(depth).times.60 mm (width).times.180 mm (height).times.1 mm
(thickness).
[0823] A plate (A4) with dimensions of 50 mm.times.100 mm.times.1
mm was prepared from the blow-molded container (A3) by cutting the
container barrel in the shape of a 50 mm.times.100 mm rectangle, of
which the center was at 60 mm from the bottom. Steam barrier
properties and haze of the resulting plate (A4) were measured. The
results are shown in Table 13 and Table 14.
Example 44
[0824] 0.1 part by weight of an antioxidant
(tetrakis[methylene3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methan-
e (Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts
by weight of the hydrogenated ring-open polymer (10) obtained in
Example 10 and the mixture was kneaded using a twin-screw kneader
(TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain a
pelletized resin composition (B2).
(Fabrication of Blow-Molded Container)
[0825] A preform was prepared from the above pellets using a
stretching blow molding machine (manufactured by Nissei ASB Machine
Co., Ltd.) by injection molding at a cylinder temperature of
200.degree. C. and an injection mold die temperature of 60.degree.
C. Next, the preform was processed by blow molding at a preform
heating pot temperature of 100.degree. C., a blowing pressure of
0.5 MPa, and a blow die temperature of 60.degree. C. to obtain a
monolayer stretched blow-molded container (B3) with a lengthwise
stretching magnification y of 2.3 times, a horizontal stretching
magnification x of 2.1 times, and dimensions of 60 mm
(depth).times.60 mm (width).times.180 mm (height).times.1 mm
(thickness).
[0826] A plate (B4) with dimensions of 50 mm.times.100 mm.times.1
mm was prepared from the blow-molded container (B3) by cutting the
container barrel in the shape of a 50 mm.times.100 mm rectangle, of
which the center was at 60 mm from the bottom. Steam barrier
properties and haze of the resulting plate (B4) were measured. The
results are shown in Table 13 and Table 14.
Example 45
[0827] 0.1 part by weight of an antioxidant
(tetrakis[methylene3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methan-
e (Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts
by weight of the hydrogenated ring-open polymer (5) obtained in
Example 5 and the mixture was kneaded using a twin-screw kneader
(TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain a
pelletized resin composition (C2).
(Fabrication of Blow-Molded Container)
[0828] The pellets were molded by injection molding using a
stretching blow molding machine (manufactured by Nissei ASB Machine
Co., Ltd.) at a cylinder temperature of 210.degree. C. and an
injection mold die temperature of 60.degree. C., and blow molded at
a heating pot temperature of 100.degree. C., a blowing pressure of
1 MPa, and a blow die temperature of 60.degree. C. to obtain a
blow-molded container (C3) with a lengthwise stretching
magnification y of 2.3 times, a horizontal stretching magnification
x of 2.1 times, and dimensions of 60 mm (depth).times.60 mm
(width).times.180 mm (height).times.1 mm (thickness).
[0829] A plate (C4) with dimensions of 50 mm.times.100 mm.times.1
mm was prepared from the blow-molded container (C3) by cutting the
side of the container in the shape of a 50 mm.times.100 mm
rectangle, of which the center was at 60 mm from the bottom. Steam
barrier properties and haze of the resulting plate (C4) were
measured. The results are shown in Table 13 and Table 14.
Example 46
[0830] 0.1 part by weight of an antioxidant
(tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]metha-
ne (Irganox 1010 manufactured by Ciba Geigy)) was added to 100
parts by weight of the hydrogenated ring-open polymer (8) obtained
in Reference Example 1 and the mixture was kneaded using a
twin-screw kneader (TEM35 manufactured by Toshiba Machine Co.,
Ltd.) to obtain a pelletized resin composition (D2).
(Fabrication of Blow-Molded Container)
[0831] A preform was prepared from the above pellets using a
stretching blow molding machine (manufactured by Nissei ASB Machine
Co., Ltd.) by injection molding at a cylinder temperature of
200.degree. C. and an injection mold die temperature of 60.degree.
C. Next, the preform was processed by blow molding at a preform
heating pot temperature of 100.degree. C., a blowing pressure of
0.5 MPa, and a blow die temperature of 60.degree. C. to obtain a
monolayer stretched blow-molded container (D3) with a lengthwise
stretching magnification y of 2.3 times, a horizontal stretching
magnification x of 2.1 times, and dimensions of 60 mm
(depth).times.60 mm (width).times.180 mm (height).times.1 mm
(thickness).
[0832] A plate (D4) with dimensions of 50 mm.times.100 mm.times.1
mm was prepared from the blow-molded container (D3) by cutting the
container barrel in the shape of a 50 mm.times.100 mm rectangle, of
which the center was at 60 mm from the bottom. Steam barrier
properties and haze of the resulting plate (D4) were measured. The
results are shown in Table 13 and Table 14.
Example 47
[0833] 0.1 part by weight of an antioxidant
(tetrakis[methylene3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methan-
e (Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts
by weight of the hydrogenated ring-open polymer (11) obtained in
Example 6 and the mixture was kneaded using a twin-screw kneader
(TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain a
pelletized resin composition (E2).
(Fabrication of Blow-Molded Container)
[0834] A preform was prepared from the above pellets using a
stretching blow molding machine (manufactured by Nissei ASB Machine
Co., Ltd.) by injection molding at a cylinder temperature of
200.degree. C. and an injection mold die temperature of 60.degree.
C. Next, the preform was processed by blow molding at a preform
heating pot temperature of 100.degree. C., a blowing pressure of
0.5 MPa, and a blow die temperature of 60.degree. C. to obtain a
monolayer stretched blow-molded container (E3) with a lengthwise
stretching magnification y of 2.3 times, a horizontal stretching
magnification x of 2.1 times, and dimensions of 60 mm
(depth).times.60 mm (width).times.180 mm (height).times.1 mm
(thickness).
[0835] A plate (E4) with dimensions of 50 mm.times.100 mm.times.1
mm was prepared from the blow-molded container (E3) by cutting the
container barrel in the shape of a 50 mm.times.100 mm rectangle, of
which the center was at 60 mm from the bottom. Steam barrier
properties and haze of the resulting plate (E4) were measured. The
results are shown in Table 13 and Table 14.
Example 48
Fabrication of Blow-Molded Container
[0836] The pellet-like resin composition (E2) obtained in Example
47 and polyethylene terephthalate (PET: Novapet manufactured by
Mitsubishi Engineering-Plastics Corporation) were co-injected to
obtain a multilayer preform having a PET/resin composition (E2)
layer constitution. The multilayer preform was blow molded using a
stretching blow molding machine (manufactured by Nissei ASB Machine
Co., Ltd.) to obtain a blow-molded container (F3) having a layer
constitution of outer layer/inner layer/outer layer=PET/resin
composition (E2)/PET (outer layer/inner layer/outer layer=300
.mu.m/600 .mu.m/100 .mu.m) and dimensions of 60 mm (depth).times.60
mm (width).times.180 mm (height). The injection temperature when
preparing the preform was 290.degree. C.
[0837] A plate (F4) with dimensions of 50 mm.times.100 mm.times.1
mm was prepared from the blow-molded container (F3) by cutting the
side of the container in the shape of a 50 mm.times.100 mm
rectangle, of which the center was at 60 mm from the bottom. Steam
barrier properties and haze of the resulting plate (F4) were
measured. The results are shown in Table 13 and Table 14.
Example 49
Fabrication of Blow-Molded Container
[0838] The pellet-like resin composition (E2) obtained in Example
5, an ethylene-vinyl alcohol copolymer with an ethylene content of
32% (EVOH: EVAL F manufactured by Kuraray Co., Ltd.), and, as an
adhesive layer, a maleic acid-modified olefin polymer (Modic
manufactured by Mitsubishi Chemical Corp.) were blow molded using a
multilayer blow molding machine (manufactured by Tahara Machinery
Ltd.) to obtain a stretched multilayer blow-molded container (G3)
having a layer constitution of outermost layer/adhesive layer/gas
barrier layer/adhesive layer/innermost layer=resin composition
(E2)/adhesive/EVOH/adhesive/resin composition (E2) (outermost
layer/adhesive layer/gas barrier layer/adhesive layer/innermost
layer=500 .mu.m/20 .mu.m/60 .mu.m/20 .mu.m/400 .mu.m) and
dimensions of 60 mm (depth).times.60 mm (width).times.180 mm
(height).
[0839] A plate (G4) with dimensions of 50 mm.times.100 mm.times.1
mm was prepared from the blow-molded container (G3) by cutting the
container barrel in the shape of a 50 mm.times.100 mm rectangle, of
which the center is at 60 mm from the bottom. Steam barrier
properties and haze of the resulting plate (G4) were measured. The
results are shown in Table 13 and Table 14.
Comparative Example 23
[0840] An autoclave equipped with a stirrer was charged with 33.4
parts by weight of a 70 wt % 2-norbornene solution in toluene, 2.86
parts by weight of dicyclopentadiene, 0.020 parts by weight of
1-hexene, and 49.3 parts by weight of cyclohexane, and the mixture
was stirred. Then, a solution containing 0.023 parts by weight of
bis(tricyclohexylphosphine)benzylidyneruthenium (IV) dichloride in
8.6 parts by weight of toluene was added, and the reaction was
carried out at 60.degree. C. for 30 minutes. The polymerization
conversion rate was about 100%. The weight average molecular weight
(Mw) of the resulting ring-open polymer (25) was 81,000, and the
molecular weight distribution (Mw/Mn) was 3.6.
(Hydrogenation Reaction)
[0841] 0.020 parts by weight of ethyl vinyl ether was added to the
polymer solution obtained above and the mixture was stirred,
followed by a hydrogenation reaction under hydrogen pressure of 1.0
MPa at 150.degree. C. for 20 hours. After cooling to room
temperature, a suspension of 0.5 parts by weight of activated
carbon in 10 parts by weight of cyclohexane was added and the
mixture was reacted under hydrogen pressure of 1.0 MPa at
150.degree. C. for two hours. The reaction mixture was filtered
through a filter with a pore diameter of 0.2 .mu.m to remove
activated carbon. The reaction solution was poured into a large
amount of isopropanol to cause the polymer to completely
precipitate. The precipitate was collected by filtration. After
washing with acetone, the hydrogenated product was dried in a
vacuum dryer at 100.degree. C. under 0.13.times.10.sup.3 Pa for 48
hours to obtain a hydrogenated ring-open polymer (20).
(Properties of Polymer)
[0842] The degree of hydrogenation of the resulting hydrogenated
ring-open polymer (20) was 99.9%, the weight average molecular
weight (Mw) was 85,000, the molecular weight distribution (Mw/Mn)
was 3.9, the isomerization ratio was 0%, and the melting point was
101.degree. C.
(Preparation of Resin Composition)
[0843] 0.1 part by weight of an antioxidant
(tetrakis[methylene3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methan-
e (Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts
by weight of the hydrogenated ring-open polymer (20) and the
mixture was kneaded using a twin-screw kneader to obtain a
pelletized resin composition (H2).
(Fabrication of Blow-Molded Container)
[0844] A preform was prepared from the above pellets using a
stretching blow molding machine (manufactured by Nissei ASB Machine
Co., Ltd.) by injection molding at a cylinder temperature of
200.degree. C. and an injection mold die temperature of 60.degree.
C. Next, the preform was processed by blow molding at a preform
heating pot temperature of 100.degree. C., a blowing pressure of
0.5 MPa, and a blow die temperature of 60.degree. C. to obtain a
monolayer stretched blow-molded container (H3) with a lengthwise
stretching magnification y of 2.3 times, a horizontal stretching
magnification x of 2.1 times, and dimensions of 60 mm
(depth).times.60 mm (width).times.180 mm (height).times.1 mm
(thickness).
[0845] A plate (H4) with dimensions of 50 mm.times.100 mm.times.1
mm was prepared from the blow-molded container (H3) by cutting the
container barrel in the shape of a 50 mm.times.100 mm rectangle, of
which the center was at 60 mm from the bottom. Steam barrier
properties and haze of the resulting plate (H4) were measured. The
results are shown in Table 13 and Table 14.
Comparative Example 24
[0846] 0.1 part by weight of an antioxidant
(tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]metha-
ne (Irganox 1010 manufactured by Ciba Geigy)) was added to 100
parts by weight of the hydrogenated ring-open polymer (9) obtained
in Comparative Example 3 and the mixture was kneaded using a
twin-screw kneader (TEM35 manufactured by Toshiba Machine Co.,
Ltd.) to obtain a pelletized resin composition (12).
(Fabrication of Blow-Molded Container)
[0847] A preform was prepared from the above pellets using a
stretching blow molding machine (manufactured by Nissei ASB Machine
Co., Ltd.) by injection molding at a cylinder temperature of
300.degree. C. and an injection mold die temperature of 120.degree.
C. Next, the preform was processed by blow molding at a preform
heating pot temperature of 250.degree. C., a blowing pressure of
0.5 MPa, and a blow die temperature of 120.degree. C. to obtain a
monolayer stretched blow-molded container (13) with a lengthwise
stretching magnification y of 2.3 times, a horizontal stretching
magnification x of 2.1 times, and dimensions of 60 mm
(depth).times.60 mm (width).times.180 mm (height).times.1 mm
(thickness).
[0848] A plate (14) with dimensions of 50 mm.times.100 mm.times.1
mm was prepared from the blow-molded container (13) by cutting the
side of the container in the shape of a 50 mm.times.100 mm
rectangle, of which the center was at 60 mm from the bottom. Steam
barrier properties and haze of the resulting plate (14) were
measured. The results are shown in Table 13 and Table 14.
Comparative Example 25
[0849] 0.1 part by weight of an antioxidant
(tetrakis[methylene3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methan-
e (Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts
by weight of the hydrogenated ring-open polymer (16) obtained in
Comparative Example 5 and the mixture was kneaded using a
twin-screw kneader (TEM35 manufactured by Toshiba Machine Co.,
Ltd.) to obtain a pelletized resin composition (J2).
[0850] A preform was prepared from the above pellets using a
stretching blow molding machine (manufactured by Nissei ASB Machine
Co., Ltd.) by injection molding at a cylinder temperature of
200.degree. C. and an injection mold die temperature of 60.degree.
C. Next, the preform was processed by blow molding at a preform
heating pot temperature of 100.degree. C., a blowing pressure of
0.5 MPa, and a blow die temperature of 60.degree. C. to obtain a
monolayer stretched blow-molded container (J3) with a lengthwise
stretching magnification y of 2.3 times, a horizontal stretching
magnification x of 2.1 times, and dimensions of 60 mm
(depth).times.60 mm (width).times.180 mm (height).times.1 mm
(thickness).
[0851] A plate (J4) with dimensions of 50 mm.times.100 mm.times.1
mm was prepared from the blow-molded container (J3) by cutting the
container barrel in the shape of a 50 mm.times.100 mm rectangle, of
which the center is at 60 mm from the bottom. Steam barrier
properties and haze of the resulting plate (J4) were measured. The
results are shown in Table 13 and Table 14.
TABLE-US-00013 TABLE 13 Blow Hydrogenated ring-open polymer molded
Melting container Monomer Hydrogenation Mw/ Isomerization Point
Pellet code No. (wt %) rate (%) Mw Mn rate (%) (.degree. C.) Code
code Example 43 A3 1 2-NB 99.9 82,200 2.9 5 140 A1 A2 (100) 44 B3
15 2-NB/DCP 99.9 81,300 3.8 9 134 B1 B2 (96/4) 45 C3 5 2-NB 99.9
185,000 4.4 10 136 C1 C2 (100) 46 D3 8 2-NB 99.75 64,200 1.3 0 143
D1 D2 (100) 47 E3 11 2-NB/MNB 99.9 100,000 2.9 8 136 E1 E2 (98/2)
48 F3 11 2-NB/MNB 99.9 100,000 2.9 8 136 E1 E2 (98/2) 49 G3 11
2-NB/MNB 99.9 100,000 2.9 8 136 E1 E2 (98/2) Comparative 23 H3 20
2-NB/DCP 99.9 85,000 3.9 0 101 H1 H2 Example (89/11) 24 I3 9 DCP --
-- -- -- 273 I1 I2 (100) 25 J3 16 MTD/DCP 99.9 55,000 2.9 -- Tg =
140.degree. C. J1 J2 (80/20)
TABLE-US-00014 TABLE 14 Blow molded container Steam barrier Blow
moldability Layer constitution properties Falling standard
deviation Haze (thickness: .mu.m) (g/(m.sup.2 24 h)) strength*
(.sigma.) Oil resistance (%) Example 43 A2 0.023 28/30 0.05 mm Not
whitened .ltoreq.20 (1000) 44 B2 0.030 30/30 0.05 mm Not whitened
.ltoreq.20 (1000) 45 C2 0.031 30/30 0.15 mm Very slightly whitened
at .ltoreq.20 (1000) the bottom 46 D2 0.023 24/30 0.30 mm Not
whitened .ltoreq.20 (1000) 47 E2 0.023 30/30 0.05 mm Not whitened
.ltoreq.20 (1000) 48 PET/E2/PET 0.037 30/30 0.10 mm Not whitened
.ltoreq.10 (300/600/100) 49 E2/AD/EVOH/AD/E2 0.025 30/30 0.10 mm
Not whitened .ltoreq.20 (500/20/60/20/400) Comparative 23 H2 0.081
30/30 0.05 mm Not whitened .ltoreq.20 Example (1000) 24 I2 0.050
18/30 0.25 mm Not whitened .gtoreq.50 (1000) 25 J2 0.110 28/30 0.05
mm Clouded .ltoreq.5 (1000) *Falling strength: Number of no cracked
or leaking containers out of 30 containers
[0852] It can be seen from Tables 13 and 14 that the moisture
permeability of the stretched blow molded containers of Examples 43
to 49 was 0.045 g/(m.sup.224 h) or less, indicating excellent steam
barrier properties.
[0853] The moisture permeability of the stretched blow molded
container of Comparative Example 26 was 0.050 g/(m.sup.224 h),
indicating slightly poor steam barrier properties.
[0854] On the other hand, the moisture permeability of the
stretched blow molded containers of Comparative Examples 23 and 25
was 0.080 g/(m.sup.224 h), indicating poor steam barrier
properties.
[0855] No cracks or leaks were observed in the stretched blow
molded containers of Examples 44, 45, and 47 to 49, and the
stretched blow molded container of Comparative Example 23 in a test
where 30 containers were caused to fall from a height of 1 m,
indicating excellent falling strength.
[0856] On the other hand, the stretched blow molded container of
Comparative Example 24 showed poor falling strength.
[0857] The stretched blow molded containers of Examples 43 to 45
and 47 to 49, and the stretched blow molded containers of
Comparative Examples 23 and 25 exhibited excellent blow
moldability.
[0858] The stretched blow molded containers of Examples 43, 44, and
46 to 49, and the stretched blow molded containers of Comparative
Examples 23 and 24 exhibited remarkably excellent oil resistance.
The stretched blow molded container of Comparative Example 25
showed poor oil resistance.
[0859] The stretched blow molded containers of Examples 43 to 49
had a haze value of 20% or less, indicating their excellent
transparency. The stretched blow molded container of Example 48
particularly had a haze value of 10% or less, indicating very good
transparency. The stretched blow molded container of Comparative
Example 24 had a haze value of 50% or more, indicating poor
transparency.
[0860] Based on the above results, the blow molded containers of
Examples 43 to 49 can be regarded to be excellent in all
performance, including steam barrier properties, mechanical
properties, processability, oil resistance, and transparency
demanded in recent years in the fields of information processing,
food industries, medical supplies, engineering works, and the
like.
Example 50
[0861] The Antioxidant A was added to and dissolved in a colorless
transparent solution of a hydrogenated ring-open polymer (1)
obtained in the same manner as in Example 1 in an amount of 0.1
part by weight per 100 parts by weight of the polymer solid
component.
[0862] The solution was filtered through a metal fiber filter (pore
diameter: 0.5 .mu.m, manufactured by Nichidai Filter Corporation)
and the filtrate was filtered through another filter Zeta Plus
Filter 30S (pore diameter: 0.5 to 1 .mu.m manufactured by Quno
Corp.). The resulting filtrate was further filtered through still
another metal fiber filter (pore diameter: 0.2 .mu.m, manufactured
by Nichidai Filter Corporation) to remove foreign matter. The
finally obtained filtrate was heated to 200.degree. C. using a
preheater and continuously supplied to a thin film dryer under a
pressure of 3 MPa (manufactured by Hitachi, Ltd.). The thin film
dryer was operated under conditions of a pressure of 13.4 kPa or
less and a temperature of the concentrated polymer solution in the
drier of 240.degree. C. (first drying step).
[0863] Next, the concentrated solution was continuously removed
from the thin film drier and supplied to another thin film drier of
the same type under a pressure of 1.5 MPa while maintaining the
temperature at 240.degree. C. This dryer was operated under the
conditions of a pressure of 0.7 kPa and a temperature of
240.degree. C. (second drying step).
[0864] The polymer was continuously removed from the thin film
drier in a melted state, extruded from a mold die in a class 100
clean room, cooled with water, and cut using a pelletizer (OSP-2
manufactured by Osada Seisakusho Co., Ltd.) to obtain pellets of a
molding material (A).
[0865] The amount of organic substances released from the molding
material (A) and the transition metal content of the molding
material (A) were measured. The results are shown in Table 15.
(Preparation of Wafer Carrier)
[0866] The molding material (A) was injected using an injection
molding machine (manufactured by Fanuc, Ltd.) under the conditions
of a cylinder temperature of 240.degree. C., a die temperature of
120.degree. C., an injection speed of 50 cm.sup.3/s, an injection
pressure of 1.47.times.10.sup.8 Pa, a support pressure of
9.8.times.10.sup.7 Pa, and a back pressure of 6.9.times.10.sup.6 Pa
to obtain an 8 inch wafer carrier (A) shown in FIG. 1.
[0867] The amount of increased foreign matter and heat resistance
of the resulting wafer carrier (A) were evaluated. The results are
shown in Table 15.
Example 51
[0868] A solution containing a hydrogenated ring-open polymer (15)
obtained in the same manner as in Example 10 was prepared. A
molding material (B) was obtained in the same manner as in Example
50 using the solution of the hydrogenated ring-open polymer
(15).
[0869] The amount of organic substances released from the molding
material (B) and the transition metal content of the molding
material (B) were measured. The results are shown in Table 15.
(Preparation of Wafer Carrier)
[0870] A wafer carrier (B) was prepared in the same manner as in
Example 50, except for using the molding material (B) instead of
the molding material (A).
[0871] The amount of increased foreign matter and heat resistance
of the resulting wafer carrier (B) were evaluated. The results are
shown in Table 15.
Example 52
[0872] A solution containing a hydrogenated ring-open polymer (11)
obtained in the same manner as in Example 6 was prepared. A molding
material (C) was obtained in the same manner as in Example 50 using
the solution of the hydrogenated ring-open polymer (11).
[0873] The amount of organic substances released from the molding
material (C) and the transition metal content of the molding
material (C) were measured. The results are shown in Table 15.
(Preparation of Wafer Carrier)
[0874] A wafer carrier (C) was prepared in the same manner as in
Example 50, except for using the molding material (C) instead of
the molding material (A). The amount of increased foreign matter
and heat resistance of the resulting wafer carrier (C) were
evaluated. The results are shown in Table 15.
Comparative Example 26
[0875] The Antioxidant A was added to a solution of a hydrogenated
ring-open polymer (20) obtained in the same manner as in
Comparative Example 23 in an amount of 0.5 parts by weight per 100
parts by weight of the polymer. A molding material (D) was obtained
in the same manner as in Example 50.
[0876] The amount of organic substances released from the resin
composition (D) and the transition metal content of the resin
composition (D) were measured. The results are shown in Table
15.
(Preparation of Wafer Carrier)
[0877] A wafer carrier (D) was prepared in the same manner as in
Example 50, except that the molding material (D) was used instead
of the molding material (A) and the cylinder temperature and the
die temperature were respectively 210.degree. C. and 80.degree.
C.
[0878] The amount of increased foreign matter and heat resistance
of the resulting wafer carrier (D) were evaluated. The results are
shown in Table 15.
Comparative Example 27
Ring-Opening Copolymerization and Hydrogenation Reaction
[0879] Polymerization and hydrogenation reactions were carried out
in the same manner as in Comparative Example 23, except that
6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene
(hereinafter referred to from time to time as "MDO") was used
instead of 2-norbornene, and the amount of 1-hexene used was 0.40
parts by weight, and a hydrogenated ring-open polymer (21) was
obtained.
(Properties of Polymer)
[0880] The degree of hydrogenation of the resulting hydrogenated
ring-open polymer (21) was 99.9%, the weight average molecular
weight (Mw) was 70,000, the molecular weight distribution (Mw/Mn)
was 2.5, the glass transition temperature was 140.degree. C., and a
melting point was not observed.
(Preparation of Resin Composition)
[0881] A molding material (E) was obtained in the same manner as in
Example 50 using the solution of the hydrogenated ring-open polymer
(21), except that the thin film drier was operated at 260.degree.
C. in the first drying step and at 270.degree. C. in the second
drying step.
[0882] The amount of organic substances released from the molding
material (E) and the transition metal content of the molding
material (E) were measured. The results are shown in Table 15.
(Preparation of Wafer Carrier)
[0883] A wafer carrier (E) was prepared in the same manner as in
Example 50, except that the molding material (E) was used instead
of the molding material (A) and the cylinder temperature and the
die temperature were respectively 300.degree. C. and 130.degree.
C.
[0884] The amount of increased foreign matter and heat resistance
of the resulting wafer carrier (E) were evaluated. The results are
shown in Table 15.
TABLE-US-00015 TABLE 15 Hydrogenated ring-open polymer Melting
Isom- Organic Transition Foreign Molding Monomer Mw/ point
erization substances metal Wafer Heat matter material (wt %) No. Mw
Mn (.degree. C.) rate (%) (ppb) (ppm) carrier resistance increase*
Example 50 A 2-NB 1 82,200 2.9 140 5 6 <1 A Good 220 (100) 51 B
2-NB/DCPD 15 81,300 3.8 134 9 8 <1 B Good 210 (96/4) 52 C
2-NB/MNB 11 100,000 2.9 136 8 6 <1 C Good 180 (98/2) Comparative
26 D 2-NB/DCPD 20 85,000 3.9 101 0 60 <1 D Bad 250 Example
(89/11) 27 E MDO 21 70,000 2.5 140 -- 35 <1 E Good 1800 (100)
*Number of foreign matter particles
[0885] As can be seen from Table 15, the wafer carriers of Examples
50 to 52 exhibited excellent heat resistance and the amounts of
discharged organic substances and increased foreign matter were
smaller than the corresponding amounts of the wafer carriers of
Comparative Examples 26 and 27. On the other hand, the wafer
carrier of Comparative Example 26 exhibited poor heat resistance
and the wafer carrier of Comparative Example 27 exhibited a
particularly large increase in the amount of foreign matter.
INDUSTRIAL APPLICABILITY
[0886] The hydrogenated ring-open polymer and the resin composition
of the present invention are useful as a resin material for molding
which is excellent in all performance, including steam barrier
properties, heat resistance, oil resistance, mechanical properties,
transparency and processability demanded in recent years in the
fields of information processing, food industries, medical
supplies, engineering works, and the like.
[0887] Since the molded article of the present invention has
excellent heat resistance, discharges only a small amount of
organic substances, and generates only a small amount of foreign
matter, the molded article can be suitably used as a material for
fabricating electron processing instruments.
[0888] The resin film and sheet of the present invention are useful
as a film or a sheet used in the fields of information processing,
food industries, medical supplies, engineering works, and the like,
since the resin film and sheet exhibit excellent performance,
including steam barrier properties, heat resistance, oil
resistance, mechanical properties, transparency, and
processability.
[0889] The multilayer laminate of the present invention is useful
as a wrapping material for toys, household goods, and the like, in
addition to packing material in the fields of foods, medical
supplies, displays, energy, and other industrial fields. A packing
material with a desired shape and size can be prepared by secondary
fabrication of the multilayer laminate of the present
invention.
[0890] Due to the possession of excellent steam barrier properties
and impact resistance, the packing material of the present
invention is useful as a medical supply container and the like such
as an infusion solution bag, a PTP (press through package), a
syringe and the like.
[0891] The blister molded article of the present invention is
useful as a container, a blister pack, or the like for medical
supplies such as a press through package (PTP), a syringe, and the
like; foods; precision components such as electric and electronic
parts, semiconductor parts, and printed circuit boards; solar
energy power generation system components; fuel cell components;
alcohol-containing fuel system components; and the like.
[0892] Due to the possession of those various characteristics, the
blow molded container of the present invention can be suitably used
as various containers demanded in recent years in the fields of
food industries, medical supplies, engineering works, and the
like.
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