U.S. patent application number 12/991757 was filed with the patent office on 2011-04-21 for resin composition and multilayer structure using same.
This patent application is currently assigned to Kuraray Co., Ltd.. Invention is credited to Osamu Kazeto.
Application Number | 20110091734 12/991757 |
Document ID | / |
Family ID | 42316929 |
Filed Date | 2011-04-21 |
United States Patent
Application |
20110091734 |
Kind Code |
A1 |
Kazeto; Osamu |
April 21, 2011 |
RESIN COMPOSITION AND MULTILAYER STRUCTURE USING SAME
Abstract
A resin composition, comprising: apolyolefin (A); a saponified
ethylene-vinyl acetate copolymer (EVOH) (B) having an ethylene
content of 20 to 65 mol % and having a degree of saponification of
vinyl acetate units of 96% or more; a higher fatty acid metal salt
(C) having 8 to 22 carbon atoms; a conjugated polyene compound (D)
having a boiling point of 20.degree. C. or higher; an
ethylene-vinyl acetate copolymer (E); and a saponified
ethylene-vinyl acetate copolymer (F) having an ethylene content of
68 to 98 mol % and having a degree of saponification of vinyl
acetate units of 200 or more, wherein the mass ratio (A:B) of the
polyolefin (A) and the EVOH (B) is 60:40 to 99.9:0.1, the amount of
the higher fatty acid metal salts (C) is in the range of 0.0001 to
10 parts by mass per 100 parts by mass of the total of the
polyolefin (A) and the EVOH (B), the amount of conjugated polyene
compound (D) is in the range of 0.000001 to 1 part by mass, and the
total amount of the ethylene-vinyl acetate copolymer (E) and the
saponified ethylene-vinyl acetate copolymer (F) is 0.3 part by mass
or more. This enables improvement of poor appearance of a molded
article caused by insufficient dispersion of the EVOH (B) at the
time of melt molding a resin composition comprising the polyolefin
(A) and the EVOH (B).
Inventors: |
Kazeto; Osamu; (Okayama,
JP) |
Assignee: |
Kuraray Co., Ltd.
Kurashiki-shi, Okayama
JP
|
Family ID: |
42316929 |
Appl. No.: |
12/991757 |
Filed: |
March 29, 2010 |
PCT Filed: |
March 29, 2010 |
PCT NO: |
PCT/JP2010/055594 |
371 Date: |
November 9, 2010 |
Current U.S.
Class: |
428/520 ;
524/394 |
Current CPC
Class: |
C08J 3/226 20130101;
C08L 2310/00 20130101; C08J 2431/04 20130101; Y10T 428/31928
20150401; B29C 48/21 20190201; C08L 2205/08 20130101; C08L 23/02
20130101; C08L 23/12 20130101; C08L 2207/066 20130101; C08J 2431/00
20130101; C08J 2429/04 20130101; C08L 2666/02 20130101; C08L
2205/02 20130101; C08L 29/04 20130101; C08J 2423/00 20130101; C08L
23/02 20130101; C08J 2323/12 20130101; C08L 23/06 20130101; C08J
2423/06 20130101; C08L 23/0853 20130101; B29K 2023/086 20130101;
C08L 2666/02 20130101; C08L 23/0861 20130101; C08L 2207/066
20130101; C08L 23/06 20130101; C08J 3/005 20130101; C08L 2666/02
20130101; C08K 5/098 20130101; C08L 23/0861 20130101; C08L 2205/06
20130101; C08L 23/0853 20130101; B29K 2023/083 20130101; B29K
2023/0633 20130101; C08L 2666/02 20130101; C08J 2423/08 20130101;
C08L 2205/035 20130101; C08K 5/098 20130101 |
Class at
Publication: |
428/520 ;
524/394 |
International
Class: |
C08K 5/098 20060101
C08K005/098; B32B 27/08 20060101 B32B027/08 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 1, 2009 |
JP |
2009-089133 |
Claims
1. A resin composition, comprising: a polyolefin (A); a saponified
ethylene-vinyl acetate copolymer (B) having an ethylene content of
20 to 65 mol % and a degree of saponification of vinyl acetate
units of 96% or more; a higher fatty acid metal salt (C) having 8
to 22 carbon atoms; a conjugated polyene compound (D) having a
boiling point of 20.degree. C. or higher; an ethylene-vinyl acetate
copolymer (E); and a saponified ethylene-vinyl acetate copolymer
(F) having an ethylene content of 68 to 98 mol % and having a
degree of saponification of vinyl acetate units of 20% or more;
wherein: a mass ratio (A:B) of the polyolefin (A) to the saponified
ethylene-vinyl acetate copolymer (B) is from 60:40 to 99.9:0.1; an
amount of the higher fatty acid metal salt (C) is from 0.0001 to 10
parts by mass per 100 parts by mass of a total of the polyolefin
(A) and the saponified ethylene-vinyl acetate copolymer (B); an
amount of the conjugated polyene compound (D) is from 0.000001 to 1
part by mass per 100 parts by mass of the total of the polyolefin
(A) and the saponified ethylene-vinyl acetate copolymer (B); and a
total amount of the ethylene-vinyl acetate copolymer (E) and the
saponified ethylene-vinyl acetate copolymer (F) is at least 0.3
parts by mass per 100 parts by mass of the total of the polyolefin
(A) and the saponified ethylene-vinyl acetate copolymer (B).
2. The resin composition according to claim 1, wherein a mass ratio
(E:F) of the ethylene-vinyl acetate copolymer (E) to the saponified
ethylene-vinyl acetate copolymer (F) is from 99.9:0.1 to
70.0:30.0.
3. The resin composition according to claim 1, wherein the
composition is prepared by: preparing a master batch by
melt-blending the higher fatty acid metal salt (C), the
ethylene-vinyl acetate copolymer (E), and the saponified
ethylene-vinyl acetate copolymer (F); and melt-blending the master
batch, the polyolefin (A), the saponified ethylene-vinyl acetate
copolymer (B), and the conjugated polyene compound (D).
4. The resin composition according to claim 1, wherein the
composition is prepared by: preparing a master batch by
melt-blending the polyolefin (A), the higher fatty acid metal salt
(C), the ethylene-vinyl acetate copolymer (E), and the saponified
ethylene-vinyl acetate copolymer (F); and melt-blending the master
batch, the polyolefin (A), the saponified ethylene-vinyl acetate
copolymer (B), and the conjugated polyene compound (D).
5. The resin composition according to claim 3, wherein: analysis of
the master batch by nuclear magnetic resonance spectroscopy
(.sup.1H-NMR) shows a signal strength ratio (Ja:Jb) of from
99.5:0.5 to 70.0:30.0; Ja is a signal derived from hydrogen atoms
bonded to carbon atoms to which acetoxy groups are bonded; and Jb
is a signal derived from hydrogen atoms bonded to carbon atoms to
which hydroxyl groups are bonded.
6. The resin composition according to claim 1, further comprising a
hydrotalcite (G) in an amount of from 0.0001 to 10 parts by mass
per 100 parts by mass of the total of the polyolefin (A) and the
saponified ethylene-vinyl acetate copolymer (B).
7. A multilayer structure, comprising: a layer made of the resin
composition according to claim 1; and a layer made of a saponified
ethylene-vinyl acetate copolymer having an ethylene content of 20
to 65 mol % and having a degree of saponification of vinyl acetate
units of 96% or more.
8. The resin composition according to claim 4, wherein: analysis of
the master batch by nuclear magnetic resonance spectroscopy
(.sup.1H-NMR) shows a signal strength ratio (Ja:Jb) of from
99.5:0.5 to 70.0:30.0; Ja is a signal derived from hydrogen atoms
bonded to carbon atoms to which acetoxy groups are bonded; and Jb
is a signal derived from hydrogen atoms bonded to carbon atoms to
which hydroxyl groups are bonded.
Description
TECHNICAL FIELD
[0001] The present invention relates to a resin composition
comprising a polyolefin, and a saponified ethylene-vinyl acetate
copolymer (may be abbreviated as EVOH hereinafter) which is
improved in preventing the formation of film surface anomalies
arising from insufficient dispersion of EVOH at the time of melt
molding the resin compositions, more specifically to a resin
composition which is improved in formation of EVOH aggregates at a
micro-scale level and formation of wavy patterns on the surface of
molded articles; and relates also to a multilayer structure
including a layer comprising such a resin composition.
BACKGROUND ART
[0002] Resin compositions made by blending polyolefins and EVOH are
well known (see Patent Document 1). However, these resin
compositions are generally poor in compatibility with each other
and, hence, when formed into film, sheet, bottle or the like by
extrusion molding, the compositions tend to generate nonuniform
phase-separated foreign matters. The number of the foreign matters
increases particularly during long periods of operation and the
appearance of the molded articles is significantly impaired
(reduction of long-run processability). Additional problems, such
as formation of lip stain around the die exit at the time of the
extrusion process of the resin compositions, are also known. This
lip stain can become mixed in the molded articles, lowering their
quality.
[0003] It is known that blending higher fatty acid metal salts
having 8 to 22 carbon atoms, ethylenediaminetetraacetate metal
salts, and/or such as hydrotalcite compounds is effective in
improving the insufficient compatibility between polyolefin and
EVOH (see Patent Documents 1 and 2). In addition to the
combination, it is disclosed that, in addition to blending
hydrotalcite based compounds and higher fatty acid metal salts
having 8 carbon atoms or more in the mixture of a polyolefin and an
EVOH, the addition of boron compounds, phosphoric acids and/or
alkali (alkali-earth) hydrogen phosphates, or lower fatty acid
metal salts having 7 carbon atoms or less, or the like, improves
long-run processability and heat resistance of compositions mainly
comprising a polyolefin and an EVOH at the time of melt molding
(physical property retention at repeated heating accompanying
recycling) (see Patent Documents 3, 4 and 5). In these documents,
however, the evaluation of fish-eye formation at the time of film
molding is done by observing the number of fish-eye particles
having a diameter of 0.2 mm or more formed per 100 cm.sup.2.
[0004] It is also disclosed that saponified ethylene-vinyl acetate
copolymers having an ethylene content of 68 to 98 mol % and having
a degree of saponification of vinyl acetate units of 20% or more
(may be abbreviated as S-EVOH hereinafter) may be blended as resin
compositions capable of preventing wavy pattern formation on the
molded articles surface in addition to using at least one component
selected from higher fatty acid metal salts having 8 to 22 carbon
atoms, ethylenediaminetetraacetate metal salts, and hydrotalcites
described above to a polyolefin and an EVOH, at the time of
melt-molding resin compositions comprising a polyolefin and an
EVOH. The wavy patterns arise from flow anomalies due to
insufficient compatibility at the time of melt molding. In this
manner, the compatibility of the obtained resin compositions is
improved and the wavy patterns on the molded article surface are
prevented, and thus the effective reuse of scrap compositions such
as regrinds is disclosed (see Patent Document 6).
[0005] It has also been disclosed that by adding an acid
graft-modified polyolefin based resin and a polyalcohol compound to
recycled materials of layered products including thermoplastic
resin layers and EVOH layers, the resin compositions showing no
gelation at the time of melt molding, producing no wavy patterns or
fish-eyes on the molded articles, having an excellent long-run
processability, and capable of preventing the phase-separated
foreign matter (lip stain), can be obtained (see Patent Document
7). However, in this document, evaluation of fish-eye formation is
done by observing the number of fish-eye particles having a
diameter of 0.4 mm or more formed per 100 cm.sup.2 in the regrind
layer of the layered products.
[0006] In addition, a method for manufacturing vinyl acetate based
polymers by the addition of a conjugated polyene compound having a
boiling point of 20.degree. C. or more to an ethylene-vinyl acetate
copolymer, and a method for manufacturing saponified vinyl acetate
based polymers by the saponification of the vinyl acetate based
polymers obtained in this method, have also been disclosed. EVOH
obtained by these methods is considered of high quality showing
minimal coloration and minimal formation of gel-like hard spots at
the time of molding (see Patent Document 8).
[0007] Also, resin compositions made by blending EVOH with an
ethylene-vinyl acetate copolymer having an ethylene content of 60
to 98 mol % and S-EVOH, and multilayer structures consisting of at
least 2 layers including the resin composition layers, have been
disclosed. According to this reference, resin compositions having
excellent gas barrier properties and improved flexibility and
transparency can be obtained (see Patent Document 9).
[0008] According to the arts disclosed in Patent Documents 2 to 7,
compatibility between EVOH and polyolefin in the resin compositions
made by blending polyolefin and EVOH can be greatly improved,
resulting in improved appearance of the molded articles. However,
in the current environment-responsive trend (volume reduction of
packaging materials and waste materials), demand for thinning of
cups, bottles and films is on the increase. Therefore, the need for
reducing the poor appearance due to insufficient dispersion at a
more micro-scale level and flow anomalies of resin compositions
made by blending polyolefin and EVOH is also increasing. For
traditional packaging materials, which were relatively thick, there
were no such problems because of the low transparency and the like.
In Patent Document 8, the art of reducing the gel-like hard spots
in molded articles made of EVOH alone is disclosed. In Patent
Document 9, the art of improving the flexibility of molded articles
made mainly of EVOH alone is disclosed. No mention or hint of resin
compositions made by blending EVOH and polyolefin is found in
Patent Documents 8 and 9.
[Prior Art Documents]
[Patent Document]
[Patent Document 1]
[0009] Laid-open Japanese patent publication No. S60-199040
[Patent Document 2]
[0010] Laid-open Japanese patent publication No. H6-87195
[Patent Document 3]
[0011] Laid-open Japanese patent publication No. H10-001569
[Patent Document 4]
[0012] Laid-open Japanese patent publication No. H10-001570
[Patent Document 5]
[0013] Laid-open Japanese patent publication No. H09-278952
[Patent Document 6]
[0014] Laid-open Japanese patent publication No. H03-72542
[Patent Document 7]
[0015] Laid-open Japanese patent publication No. 2008-115367
[Patent Document 8]
[0016] Laid-open Japanese patent publication No. H09-71620
[Patent Document 9]
[0017] Laid-open Japanese patent publication No. H03-192140
SUMMARY OF INVENTION
Problems to be Solved by the Invention
[0018] The present inventors have found that the film surface
anomalies, which appear at the time of melt molding the resin
composition made by blending a polyolefin and an EVOH, and which
impair the appearance, are caused by insufficient dispersion of
EVOH, or more specifically, the formation of EVOH aggregates at a
micro-scale level.
[0019] Accordingly, the objects of the present invention are to
improve the dispersibility of EVOH by suppressing the formation of
aggregates at a micro-scale level, to reduce the occurrences of
poor appearance such as wavy patterns on the molded article surface
caused by flow anomalies due to the aggregates, and thus to
effectively reuse the layered product comprising the polyolefin
layer and the EVOH layer, or other such as scrap portion, as a
regrind layer, and finally to obtain molded articles with good
appearance.
Means for Solving the Problem
[0020] According to the present invention, the above-described
object can be achieved by providing a resin composition comprising:
a polyolefin (A); a saponified ethylene-vinyl acetate copolymer (B)
having an ethylene content of 20 to 65 mol % and having a degree of
saponification of vinyl acetate units of 96% or more (hereinafter
simply, "EVOH (B)"); a higher fatty acid metal salt (C) having 8 to
22 carbon atoms (hereinafter simply, "higher fatty acid metal salt
(C)"); a conjugated polyene compound (D) having a boiling point of
20.degree. C. or higher (hereinafter simply, "conjugated polyene
compound (D)"); an ethylene-vinyl acetate copolymer (E)
(hereinafter, "EVAc (E)"); and a saponified ethylene-vinyl acetate
copolymer (F) having an ethylene content of 68 to 98 mol % and
having a degree of saponification of vinyl acetate units of 20% or
more (hereinafter, "S-EVOH (F)"), wherein the mass ratio (A:B) of
the polyolefin (A) and the EVOH (B) is 60:40 to 99.9:0.1, the
amount of higher fatty acid metal salts (C) is in the range of
0.0001 to 10 parts by mass per 100 parts by mass of the total of
polyolefin (A) and EVOH (B), the amount of conjugated polyene
compound (D) is in the range of 0.000001 to 1 part by mass per 100
parts by mass of the total of polyolefin (A) and EVOH (B), and the
total amount of an EVAc (E) and the S-EVOH (F) is 0.3 part by mass
or more per 100 parts by mass of the total of polyolefin (A) and
EVOH (B).
[0021] In the resin composition, it is a preferable embodiment of
the present invention that the mass ratio (E:F) between the
ethylene-vinyl acetate copolymer (E) and the saponified
ethylene-vinyl acetate copolymer (F) is in the range of 99.9:0.1 to
70.0:30.0.
[0022] In the resin composition, preferably, a master batch is
prepared in advance by melt-blending the higher fatty acid metal
salt (C) having 8 to 22 carbon atoms, the ethylene-vinyl acetate
copolymer (E), and the saponified ethylene-vinyl acetate copolymer
(F), and the resin composition is obtained by melt-blending the
master batch, the polyolefin (A), the saponified ethylene-vinyl
acetate copolymer (B), and the conjugated polyene compound (D)
having a boiling point of 20.degree. C. or higher.
[0023] Preferably, a master batch is prepared in advance by
melt-blending the polyolefin (A), the higher fatty acid metal salt
(C), the EVAc (E), and the S-EVOH (F), and the resin compositions
are obtained by melt-blending the master batch, the polyolefin (A),
the EVOH (B), and the conjugated polyene compound (D).
[0024] It is a preferable embodiment in the resin composition
according to the present invention that the master batch (obtained
above) analyzed by nuclear magnetic resonance spectroscopy
(.sup.1H-NMR) method shows a signal strength ratio (Ja:Jb) between
the signal Ja deriving from the hydrogen atoms bonded to the carbon
atoms to which acetoxy groups are bonded, and the signal Jb
deriving from the hydrogen atoms bonded to the carbon atoms to
which hydroxyl groups are bonded, in the range of 99.5:0.5 to
70.0:30.0.
[0025] A resin composition obtained as follows is also a preferable
embodiment of the present invention: a resin composition obtained
by further containing in the above resin composition a hydrotalcite
(G) in the range of 0.0001 to 10 parts by mass per 100 parts by
mass of the total of the polyolefin (A) and the EVOH (B).
[0026] A preferable embodiment of the present invention also is a
multilayer structure having at least two layers comprising a layer
made of any one of the above-described resin compositions, and a
layer made of a saponified ethylene-vinyl acetate copolymer having
an ethylene content of 20 to 65 mol % and having a degree of
saponification of vinyl acetate units of 96% or more.
ADVANTAGEOUS EFFECTS OF INVENTION
[0027] The present invention offers resin compositions capable of
suppressing the formation of EVOH aggregates at the micro-scale
levels to improve the dispersibility and reducing the occurrences
of flow anomalies caused by the aggregates. The resin composition
of the present invention can be used as a recycled regrind layer
even from scraps, etc., of layered products having the polyolefin
layer and the EVOH layer. Even in this case, molded articles
without defects in the appearance can be obtained.
DESCRIPTION OF EMBODIMENTS
[0028] The resin composition of the present invention contains
polyolefin (A), EVOH (B), higher fatty acid metal salt (C),
conjugated polyene compound (D), EVAc (E), and S-EVOH (F). The mass
ratio of polyolefin (A) and EVOH (B), (A:B), is 60:40 to 99.9:0.1.
The amount of higher fatty acid metal salts (C) contained is in the
range of 0.0001 to 10 parts by mass per 100 parts by mass of the
total of polyolefin (A) and EVOH (B). The amount of conjugated
polyene compound (D) is in the range of 0.000001 to 1 part by mass
per 100 parts by mass of the total of polyolefin (A) and EVOH (B).
The total amount of EVAc (E) and S-EVOH (F) contained is 0.3 part
by mass or more per 100 parts by mass of the total of polyolefin
(A) and EVOH (B).
[0029] Polyolefin (A) used in the present invention includes
polyethylene (low density, linear low density, medium density, and
high density); ethylene based copolymers prepared by
copolymerization of ethylene and .alpha.-olefins such as 1-butene,
1-hexene and 4-methyl-1-pentene or acrylic esters; polypropylene
(homo polypropylene, random polypropylene, block polypropylene,
etc.); propylene based copolymers prepared by copolymerization of
propylene and .alpha.-olefins such as ethylene, 1-butene, 1-hexene,
4-methyl-1-pentene; modified polypropylenes blended with rubber
based polymers; poly(1-butene), poly(4-methyl-1-pentene), modified
polypropylenes prepared by reacting the polyolefin with maleic
anhydride; and ionomer resins. In the present invention, as
polyolefins (A), it is preferable to use polypropylene based resins
of polypropylene or propylene based copolymers, or polyethylene
based resins of polyethylene or ethylene based copolymers. In
particular, it is more preferable to use polypropylene based
resins. As a polyolefin (A), one single polyolefin or two or more
mixed polyolefins may be used. When, out of these polyolefins (A),
polyolefins containing halogen compounds from polymerization
catalyst residues or existing as impurities in additives such as
fillers and pigments at a level of 1 to 300 ppm, preferably 3 to
150 ppm, in terms of halogens are used, the effect of the present
invention will be more remarkable.
[0030] EVOH (B) used in the present invention is ethylene-vinyl
acetate copolymer with its vinyl acetate units saponified
(hydrolyzed). EVOH having a relatively low ethylene content and a
high degree of saponification (degree of hydrolysis) of vinyl
acetate units tends to show poor compatibility with polyolefin. If
the ethylene content in EVOH is excessive, the gas barrier property
of the resin composition according to the present invention will be
reduced. If the degree of saponification (degree of hydrolysis) of
the vinyl acetate units in EVOH is low, the thermal stability of
the EVOH itself will be poor. From these standpoints, the ethylene
content of EVOH (B) according to the present invention is 20 to 65
mol %, or preferably 20 to 60 mol %, and more preferably 20 to 50
mol %. The degree of saponification of vinyl acetate units of EVOH
(B) is preferably 96% or more, or more preferably 98% or more, and
even more preferably 99% or more. EVOH having an ethylene content
of 20 to 65 mol % and a degree of saponification of 99% or more is
especially important as a subject matter to which the present
invention applies because it can be used to obtain containers
having excellent properties such as gas barrier property when
laminated with polyolefin (A).
[0031] The EVOH (B) may be modified with other copolymerizable
monomers to the extent that does not inhibit the effect of the
present invention, usually in the range of not more than 5 mol %.
Examples of the modifying copolymerizable monomer include
.alpha.-olefins such as propylene, 1-butene, 1-hexene, and
4-methyl-1-pentene; esters such as acrylic acid esters and
methacrylic acid esters; higher fatty acids such as maleic acid,
fumaric acid, and itaconic acid, and vinyl esters thereof; alkyl
vinyl ethers; N-(2-dimethylaminoethyl)methacrylamide or its
quaternary compounds, N-vinylimidazole or its quaternary compounds,
N-vinylpyrrolidone, N,N-butoxymethylacrylamide,
vinyltrimethoxysilane, vinylmethyldimethoxysilane,
vinyldimethylmethoxysilane, and the like.
[0032] It is desirable that the melt index (MI; measured at
190.degree. C., under a load of 2160 g) of EVOH (B) is 0.1 g/10
minutes or more, or preferably 0.5 g/10 minutes or more, and 100
g/10 minutes or less, or more preferably 50 g/10 minutes or less,
and most preferably 30 g/10 minutes or less. In this case, from the
viewpoint of the dispersibility of EVOH (B), the ratio of MI (B)/MI
(A) is preferably in the range of 0.1 to 100, and more preferably
0.3 to 50. Here, MI (B) is MI of EVOH (B) and MI (A) is MI of
polyolefin (A) (measured at 190.degree. C., under a load of 2160
g).
[0033] To realize the best effect of the present invention, it is
important to keep the mass ratio (A:B) of the polyolefin (A) and
the EVOH (B) in the resin composition according to the present
invention in the range of 60:40 to 99.9:0.1. In the mass ratio, if
EVOH (B) exists at a higher level than 60:40, the effect of
preventing the aggregation of EVOH (B) at a micro-scale level
cannot be fully realized. If polyolefin (A) exists at a higher
level than 99.9:0.1, the effect of the present invention cannot be
fully observed. From this viewpoint, it is more preferable to keep
the mass ratio (A:B) of polyolefin (A) and EVOH (B) in the range of
65:35 to 99.7:0.3.
[0034] As for higher fatty acid metal salts (C) according to the
present invention, metal salts of lauric acid, stearic acid,
myristic acid and the like can be used. As for the metal salts,
those of Group I, II, or III of the periodic table, for example,
such as sodium salt, potassium salt, calcium salt, and magnesium
salt, can be listed. Zinc salt of these fatty acids may also be
used. Of these, the metal salts of Group II of the periodic table,
such as calcium salt and magnesium salt, are preferable as they can
produce the effect of the present invention when added in a small
quantity.
[0035] If the amount of higher fatty acid metal salts (C) to be
added is too small, the effect of the present invention cannot be
realized. If an excessive amount of the salts is added, it may
promote thermal degradation of EVOH (B) and cause foaming by
decomposition gases, or coloration. For this reason, it is
preferable that the amount of higher fatty acid metal salts (C) to
be added is in the range of 0.0001 to 10 parts by mass per 100
parts by mass of the total of polyolefin (A) and EVOH (B), or more
preferable in the range of 0.001 to 1 part by mass.
[0036] Conjugated polyene compounds (D) used in the present
invention are compounds having so-called conjugating double bonds
and have a structure in which carbon-carbon double bonds and
carbon-carbon single bonds are connected alternately, with the
number of carbon-carbon double bonds being 2 or more. A conjugated
polyene compound (D) may be a conjugated diene having 2
carbon-carbon double bonds and 1 carbon-carbon single bond
connected alternately, or a conjugated triene having 3
carbon-carbon double bonds and 2-carbon-carbon single bonds
connected alternately. It may be a conjugated polyene compound
having a greater number of carbon-carbon double bonds and
carbon-carbon single bonds connected alternately. Polyenes having
fewer than 7 carbon-carbon double bonds to conjugate are preferred
as, if the number of carbon-carbon double bonds to conjugate is 8
or more, the conjugated polyene compound may color the molded
articles by its own color. Also, the polyene may contain, in one
molecule, a plurality of independent sets of conjugating double
bonds each consisting of 2 or more carbon-carbon double bonds. For
example, a compound such as wood oil that has 3 conjugated trienes
in one molecule can be included in conjugated polyene compounds
(D). Conjugated polyene compounds (D) may also contain, in addition
to conjugating double bonds, other functional groups. These
functional groups include carboxylic group and its salt, hydroxyl
group, ester group, carbonyl group, ether group, amino group, imino
group, amide group, cyano group, diazo group, nitro group, sulfonic
group, sulfoxide group, sulfide group, thiol group, sulfonic acid
group and its salt, phosphate group and its salt, phenyl group,
halogen atom, double bond, and triple bond.
[0037] Specific examples of conjugated polyene compounds (D)
include conjugated diene compounds having conjugation structures of
2 carbon-carbon double bonds such as: isoprene;
2,3-dimethyl-1,3-butadiene; 2,3-diethyl-1,3-butadiene;
2-t-butyl-1,3-butadiene; 1,3-pentadiene;
2,3-dimethyl-1,3-pentadiene; 2,4-dimethyl-1,3-pentadiene;
3,4-dimethyl-1,3-pentadiene; 3-ethyl-1,3-pentadiene;
2-methyl-1,3-pentadiene; 3-methyl-1,3-pentadiene;
4-methyl-1,3-pentadiene; 1,3-hexadiene; 2,4-hexadiene;
2,5-dimethyl-2,4-hexadiene; 1,3-octadiene; 1,3-cyclopentadiene;
1,3-cyclohexadiene; 1-phenyl-1,3-butadiene;
1,4-diphenyl-1,3-butadiene; 1-methoxy-1,3-butadiene;
2-methoxy-1,3-butadiene; 1-ethoxy-1,3-butadiene;
2-ethoxy-1,3-butadiene; 2-nitro-1,3-butadiene; chloroprene;
1-chloro-1,3-butadiene; 1-bromo-1,3-butadiene;
2-bromo-1,3-butadiene; fulvene; tropone; ocimene; phellandrene;
myrcene; farnesene; cembrene; sorbic acid; sorbic acid ester;
sorbic acid salt; and abietic acid; conjugated triene compounds
having conjugation structures of 3 carbon-carbon double bonds such
as: 1,3,5-hexatriene; 2,4,6-octatriene-1-carboxylic acid;
eleostearic acid; wood oil; and cholecarciferol; and conjugated
polyene compounds having conjugation structures of 4 or more
carbon-carbon double bonds such as: cyclooctatetraene; 2, 4, 6,
8-decatetraene-1-carboxylic acid; retinol; and retinoic acid. These
conjugated polyene compounds (D) may be used singularly or in
combinations of 2 or more compounds.
[0038] The amount of conjugated polyene compounds (D) to be added
is in the range of 0.000001 to 1 part by mass per 100 parts by mass
of the total of polyolefin (A) and EVOH (B), or more preferably in
the range of 0.00001 to 1 part by mass. If the added amount is less
than 0.00001 part by mass per 100 parts by mass of the total of
polyolefin (A) and EVOH (B), the effect of the present invention
may not be satisfactory. If the added amount is greater than 1 part
by mass per 100 parts by mass of the total of polyolefin (A) and
EVOH (B), gelation of the obtained resin compositions may be
promoted.
[0039] Conjugated polyene compound (D) may be directly blended in
the mixture of polyolefin (A) and EVOH (B). If the added amount is
very small, it may be blended in EVOH (B) with good compatibility
in advance so that it can be uniformly dispersed in the resin
composition of the present invention.
[0040] EVAc (E) used in the present invention may be random
copolymers prepared by polymerizing ethylene and vinyl acetate
according to known methods, terpolymer prepared by copolymerizing
another monomer, or modified EVAc modified by grafting. The vinyl
acetate unit content of EVAc (E) is preferably 2 to 40 mol %, or
more preferably 5 to 25 mol %. If the vinyl acetate unit content is
below 2 mol % or above 40 mol %, EVOH (B) aggregation may not be
effectively prevented. The melt index (MI; measured at 190.degree.
C., under a load of 2160 g) of EVAc (E) is preferably in the range
of 0.1 to 50 g/10 minutes, or more preferably 0.5 to 30 g/10
minutes, and even more preferably 1 to 20 g/10 minutes.
[0041] S-EVOH (F) used in the present invention is a saponified
ethylene-vinyl acetate copolymer having an ethylene content of 68
to 98 mol % and having a degree of saponification of vinyl acetate
units of 20% or more. Unlike the usual type of EVOH used for food
wrapping materials, it has high ethylene content and is capable of
significantly improving compatibility between polyolefin (A) and
EVOH (B). The ethylene content of S-EVOH (F) is preferably 70 mol %
or more, and it is preferably 96 mol % or less, or more preferably
94 mol % or less. The degree of saponification of vinyl acetate
units is preferably 30% or more, or more preferably 40% or more.
The upper limit of the degree of saponification is not strictly
defined. Materials with a degree of saponification of 99 mol % or
more or substantially 100% can also be used. If the ethylene
content is below 68 mol % or above 98 mol %, or if the degree of
saponification of vinyl acetate units is less than 20%, the effect
of the present invention will not be fully realized.
[0042] According to the specification of the present invention, the
ethylene content of S-EVOH (F) should be higher than that of EVOH
(B). The difference in the ethylene content between S-EVOH (F) and
EVOH (B) is preferably at least 10 mol % or more, and more
preferably 20 mol % or more from the standpoint of improving the
compatibility between polyolefin (A) and EVOH (B).
[0043] MI of S-EVOH (F) (measured at 190.degree. C., under a load
of 2160 g) is preferably 0.1 g/10 minutes or more, more preferably
0.5 g/10 minutes or more, and even more preferably 1 g/10 minutes
or more. At the same time, the MI of S-EVOH (F) is preferably 100
g/10 minutes or less, or more preferably 50 g/10 minutes or less,
and even more preferably 30 g/10 minutes or less. S-EVOH (F) used
in the present invention may be modified with an unsaturated
carboxylic acid or its derivatives. These unsaturated carboxylic
acids or derivatives include acrylic acid, methacrylic acid, maleic
acid, fumaric acid, itaconic acid, and maleic acid; methyl or ethyl
esters of these acids; and maleic anhydride, itaconic anhydride,
and the like. These acid monomers may be used singularly or in
combination.
[0044] The total amount of EVAc (E) and S-EVOH (F) added to the
resin composition of the present invention is 0.3 part by mass or
more per 100 parts by mass of the total of polyolefin (A) and EVOH
(B), and is preferably 0.5 part by mass or more. If the addition is
less than 0.3 part by mass, the effect of EVAc (E) and S-EVOH (F)
addition will not be fully realized. Although the upper limit of
the addition is not clearly specified, excessive addition will not
increase the dispersibility of EVOH (B) in the resin composition
above a certain limit. In a normal practice, addition of 30 parts
by mass or less will be sufficient.
[0045] In the resin composition of the present invention, the
content of EVAc (E) and S-EVOH (F) in terms of mass ratio (E:F) is
preferably in the range of 99.9:0.1 to 70.0:30.0, and more
preferably in the range of 99.5:0.5 to 85.0:15.0. In this ratio, if
the ratio of S-EVOH (F) is below those ranges, the dispersibility
of EVOH (B) in the resin composition may deteriorate and reduce the
effects of the present invention. If the proportion of S-EVOH (F)
is above those ranges, the effect of improving the dispersibility
of EVOH (B) will be lowered.
[0046] In addition to above-mentioned polyolefin (A), EVOH (B),
higher fatty acid metal salts (C), conjugated polyene compounds
(D), EVAc (E) and S-EVOH (F) that constitute the resin composition
of the present invention, hydrotalcite (G) may be added. Addition
of hydrotalcite (G) as a constituent of the resin composition of
the present invention is preferred because it improves the
dispersibility of EVOH (B) in the resin compositions.
[0047] As hydrotalcite compounds (G) employed in the present
invention, hydrotalcite complex salts shown by the following
formula can be listed.
M.sub.xAl.sub.y(OH).sub.2x+3y-2z(A).sub.z.aH.sub.2O
(where: M is one or more selected from Mg, Ca, Sr, Ba, Zn, Cd, Pb,
Sn; A is CO.sub.3 or HPO.sub.4; x, y, z are positive numbers; a is
either 0 or a positive number; 2x+3y-2z>0).
[0048] In the hydrotalcites, M is preferably Mg, Ca or Zn, and more
preferably is a combination of two or more of these metals.
Examples of particularly favorable hydrotalcites are listed
below.
Mg.sub.6Al.sub.2(OH).sub.16CO.sub.3.4H.sub.2O
Mg.sub.8Al.sub.2(OH).sub.20CO.sub.3.5H.sub.2O
Mg.sub.5Al.sub.2(OH).sub.14CO.sub.3.4H.sub.2O
Mg.sub.10Al.sub.2(OH).sub.22(CO.sub.3).sub.2.4H.sub.2O
Mg.sub.6Al.sub.2(OH).sub.16HPO.sub.4.4H.sub.2O
Ca.sub.6Al.sub.2(OH).sub.16CO.sub.3.4H.sub.2O
Zn.sub.6Al.sub.2(OH).sub.16CO.sub.3.4H.sub.2O
Mg.sub.3ZnAl.sub.2(OH).sub.12CO.sub.3.2.7H.sub.2O
Mg.sub.6Zn.sub.2Al.sub.2(OH).sub.20CO.sub.3.1.6H.sub.2O
Mg.sub.5Zn.sub.1.7Al.sub.3.3(OH).sub.20(CO.sub.3).sub.1.65.4.5H.sub.2O
[0049] When hydrotalcite (G) is further added, the added amount is
in the range of 0.0001 to 10 parts by mass per 100 parts by mass of
the total of polyolefin (A) and EVOH (B), and more preferably in
the range of 0.001 to 1 part by mass. If the added amount is less
than 0.0001 part by mass per 100 parts by mass of the total of
polyolefin (A) and EVOH (B), the effect of the present invention
may not be satisfactory. If the added amount is more than 10 parts
by mass per 100 parts by mass of the total of polyolefin (A) and
EVOH (B), it may promote thermal degradation of EVOH in the
obtained resin composition and cause foaming by decomposition
gases, or coloration.
[0050] Adding modified polyolefin resins modified with unsaturated
carboxylic acids or derivatives thereof to the resin composition of
the present invention is effective in suppressing the aggregation
of EVOH (B) at a micro-scale level. Here, modified polyolefin
resins are polyolefin resins modified with one or more of
unsaturated carboxylic acids or derivatives thereof, selected from
the following groups: unsaturated carboxylic acids such as acrylic
acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid,
itaconic acid and citraconic acid, including their esters or
anhydrides; and derivatives of unsaturated carboxylic acids such as
methyl acrylate, methyl methacrylate, ethyl acrylate, propyl
acrylate, butyl acrylate, butyl methacrylate, vinyl acetate,
glycidyl acrylate, glycidyl methacrylate, acrylamide,
methacrylamide, sodium acrylate, and sodium methacrylate. As
polyolefin resins before modification, polyethylene, polypropylene,
ethylene-vinyl acetate copolymer, and ethylene-acrylate ester
copolymers can be preferably listed.
[0051] Further, publicly known additives capable of improving
various properties such as thermal stability at the time of melt
extrusion molding of EVOH may be preferably added within the
reasonable extent that does not inhibit the effect of the present
invention as these additives may be expected to reduce the
deterioration of EVOH (B) which is a constituent of the resin
composition of the present invention. These additives include
organic acids such as acetic acid and lactic acid, inorganic acids
such as hydrochloric acid and phosphoric acid, metal salts of these
acids with metals of periodic table Groups I, II and III, boron
compounds such as boric acid, and higher fatty acids such as
stearic acid. In particular, addition of boric acid is effective to
suppress aggregation of EVOH (B), with the preferable amount to be
added ranging from 0.0001 to 0.1 part by mass per 100 parts by mass
of the total of polyolefin (A) and EVOH (B). Conversely, boric acid
added in excess of 0.1 part by mass per 100 parts by mass of the
total of polyolefin (A) and EVOH (B) may promote the aggregation of
EVOH (B).
[0052] In the following, the method of obtaining the resin
composition of the present invention by mixing the polyolefin (A),
EVOH (B), higher fatty acid metal salts (C), conjugated polyene
compounds (D), EVAc (E), and S-EVOH (F), and the method of molding
the resin compositions, will be explained.
[0053] There are no particular restrictions with respect to methods
for blending to obtain the resin composition according to the
present invention. A method wherein polyolefin (A), EVOH (B),
higher fatty acid metal salts (C), conjugated polyene compounds
(D), EVAc (E) and S-EVOH (F) are dry-blended together and then
melt-blended; and a method wherein higher fatty acid metal salts
(C) and/or conjugated polyene compounds (D) are blended in advance
in polyolefin (A) and/or EVOH (B), and the mixture is dry-blended
with the remaining components and then melt-blended; can be listed
as examples. A preferable method is the one wherein a mixture
prepared by blending polyolefin (A) and conjugated polyene
compounds (D) in EVOH (B) is dry-blended with a mixture prepared by
blending higher fatty acid metal salts (C), EVAc (E), and S-EVOH
(F), and the final mixture is melt-blended. Another preferable
method is the one wherein a mixture prepared by blending polyolefin
(A) and conjugated polyene compounds (D) with EVOH (B) is
dry-blended with another mixture prepared by blending higher fatty
acid metal salts (C), EVAc (E), and S-EVOH (F) with polyolefin (A),
and then melt-blended.
[0054] As described above, when a conjugated polyene compound (D)
is blended in EVOH (B) in advance, satisfactory results can be
obtained as to the effect of the present invention even when a
reduced amount of conjugated polyene compound (D) is added. Methods
of blending conjugated polyene compound (D) in EVOH (B) in advance
are not specified. A method is listed as an example wherein EVOH
(B) is dissolved in a good solvent of EVOH (B) such as
water/methanol mixed solvent, and a conjugated polyene compound (D)
is dissolved in this solution at a concentration level of 0.000001
to 10 parts by mass per 100 parts by mass of EVOH (B). The mixed
solution is extruded into a poor solvent through a nozzle, etc. The
deposit is precipitated, solidified, rinsed and dried to obtain
EVOH (B) blended with a conjugated polyene compound (D).
[0055] Methods for blending a higher fatty acid metal salt (C),
EVAc (E) and S-EVOH (F) in advance, and those for blending a higher
fatty acid metal salt (C), EVAc (E), and S-EVOH (F) in a polyolefin
(A) in advance are not specified. A method in which each component
is dry-blended, or a method in which each component is melt-blended
and then pelletized so as to prepare a master batch, are listed as
examples. Of these methods, the latter is more favorable to easy
handling from the standpoint that higher fatty acid metal salts (C)
are usually in a powder form.
[0056] When a sample of the master batch is analyzed by the nuclear
magnetic resonance spectroscopy (.sup.1H-NMR) method, the signal
strength ratio (Ja:Jb) is preferably in the range of 99.5:0.5 to
70.0:30.0. Here, Ja is the signal deriving from the hydrogen atoms
bonded to the carbon atoms to which acetoxy groups are bonded, and
Jb is the signal deriving from the hydrogen atoms bonded to the
carbon atoms to which hydroxyl groups are bonded. In other words,
it is preferable, from the standpoint of improving the
dispersibility of EVOH (B), that carbon atoms bonded with acetoxy
groups and carbon atoms bonded with hydroxyl groups exist in the
resin composition of the present invention, and its existing molar
ratio is in the range of 99.5:0.5 to 70.0:30.0. If the strength
ratio is either below 0.5 or above 30.0, the effect of improving
the dispersibility of EVOH (B) may not be satisfactory.
[0057] As methods for keeping the strength ratio of Ja and Jb,
i.e., (Ja:Jb), in the range of 99.5:0.5 to 70.0:30.0, a method of
adjusting the mixing ratio of EVAc (E) and S-EVOH (F) suitably, a
method of adjusting the degree of saponification of S-EVOH (F), and
a method of adjusting the ethylene content of EVAc (E) and/or
S-EVOH (F) suitably, can be listed.
[0058] There are no particular restrictions with respect to methods
for blending when adding hydrotalcite (G). A mixture of polyolefin
(A), EVOH (B), higher fatty acid metal salts (C), conjugated
polyene compounds (D), EVAc (E), and S-EVOH (F) can be dry-blended
with hydrotalcite (G) and then melt-blended. If polyolefin (A),
higher fatty acid metal salts (C), EVAc (E), and S-EVOH (F) are
melt-blended and then pelletized in advance to obtain a master
batch, hydrotalcite (G) can be blended at the same time to be
included in the pellet when the master batch is manufactured. This
treatment is preferable from the standpoint of reducing the number
of materials to be handled at the final step of melt-blending the
resin composition of the present invention.
[0059] The resin composition of the present invention may further
blend additives other than those described above to the extent that
does not inhibit the effect of the present invention. These
additives include antioxidants, ultraviolet absorbers,
plasticizers, antistatic agents, lubricants, coloring agents,
fillers and other polymeric compounds. Specific examples of
additives are shown below.
Antioxidants: 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol,
4,4'-thiobis-(6-t-butylphenol),
2,2'-methylene-bis-(4-methyl-6-t-butylphenol), octadecyl-3-(3',
5'-di-t-butyl-4'-hydroxylphenyl)propionate,
4,4'-thiobis-(6-t-butylphenol), and the like. Ultraviolet
absorbers: ethylene-2-cyano-3,3'-diphenyl acrylate,
2-(2'-hydroxyl-5'-methylphenyl)benzotriazole,
2-(2'-hydroxyl-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazo le,
2-hydroxyl-4-methoxybenzophenone,
2,2'-dihydroxyl-4-methoxybenzophenone,
2-hydroxyl-4-octoxybenzophenone, and the like. Plasticizers:
dimethyl phthalate, diethyl phthalate, dioctyl phthalate, wax,
liquid paraffin, phosphoric acid esters, and the like. Antistatic
agents: pentaerythrit monostearate, sorbitan monopalmitate,
sulfated polyolefins, polyethylene oxide, carbowax, and the like.
Lubricants: ethylenebisstearoamide, butyl stearate, and the like.
Coloring agents: titanium oxide, carbon black, phthalocyanine,
quinacrydone, indolin, azo pigments, colcothar, and the like.
Fillers: glass fiber, asbestos, balastonite, calcium silicate, and
the like.
[0060] Among these additives, coloring agents and fillers in
particular, may often contain impurities that promote aggregation
of EVOH (B) that constitutes the resin composition of the present
invention at a micro-scale level. For this reason, when these
additives are blended in, the amount of higher fatty acid metal
salts (C) and/or conjugated polyene compounds (D), and/or EVAc (E)
and/or S-EVOH (F) to be blended may have to be increased as
needed.
[0061] Many other polymeric compounds may also be blended in the
resin composition of the present invention to the extent that does
not inhibit the effect of the present invention.
[0062] As the mixing tools for each constituent to obtain the resin
composition of the present invention, ribbon blenders, high-speed
mixer-cokneaders, mixing rolls, extruders, intensive mixers, or the
like, can be listed.
[0063] The resin composition of the present invention can be molded
into desired molded articles such as films, sheets, tubes, bottles,
cups, and the like through publicly known melt extrusion molding
machines, compression molding machines, transfer molding machines,
injection molding machines, blow molding machines, heat molding
machines, rotary molding machines, dipping molding machines, and
the like. The extrusion temperature for molding is generally in the
range of 170 to 350.degree. C., although it is suitably selected
depending on the type of polyolefin (A) constituting the resin
composition of the present invention, melt indices of polyolefin
(A) and EVOH (B), composition ratio of polyolefin (A) and EVOH (B),
or type of molding machine and the like.
[0064] When the resin composition of the present invention is used
as a layer construction of a multilayer structure containing the
layer of polyolefin and the layer of EVOH, the multilayer structure
may has any layer construction with one or more layers positioned
in arbitrary positions. Such layer constructions are expressed as
in the following layer constructions, where c is the resin
composition of the present invention, a is polyolefin, b is EVOH,
and ad is adhesive resin. Here, the modified polyolefin resin,
modified with unsaturated carboxylic acids or derivatives thereof
can be preferably used as ad.
3 layers: a/c/b 4 layers: c/b/ad/a, a/c/ad/b 5 layers: c/ad/b/ad/c,
a/c/b/ad/a, a/c/b/c/a 6 layers: a/c/ad/b/ad/a 7 layers:
a/c/ad/b/ad/c/a
[0065] In these multilayer structures, the resin composition of the
present invention can be replaced with melt-blended scraps of the
multilayer structure. In addition to the multilayer structure,
scraps of other polyolefin molding can be mixed and melt-blended.
Therefore, in the case when an ad layer is used in such multilayer
structures, the resin composition of the present invention will
necessarily contain ad as a constituent.
[0066] As the multilayer structures of the layer construction
contain EVOH having a high gas barrier property, these are useful
as packaging materials for food products, medicinal products, and
medical devices, and the like, which require high gas barrier
properties.
[0067] As a method of multilayer formation, co-extrusion molding is
a favorable method. In this method, a number of separate extruders
corresponding to the number of types of resin layers are used, and
resins melted in each extruder are simultaneously co-extruded to
form a laminated layer structure. Other applicable methods are
multilayer formation methods including extrusion coating and dry
lamination, and the like. Further, molded articles having excellent
mechanical properties and excellent gas barrier properties can be
obtained by performing the stretching on the singular molded
article of the resin composition of the present invention, or the
multilayer structures containing the resin composition of the
present invention by means of monoaxial stretching, biaxial
stretching, or blow stretching.
[0068] Molded articles obtained from the resin composition of the
present invention have neat appearances and have excellent
mechanical properties and excellent gas barrier properties, as EVOH
in the resin composition of the present invention is uniformly
dispersed with its aggregation at a micro-scale level suppressed.
Thus, these articles are of great industrial value.
EXAMPLES
[0069] In the following, the present invention will be explained in
greater detail through examples. In the following manufacturing
examples, examples, and comparative examples, "part" means "part by
mass" unless otherwise specified.
[Method of Quantitative Determination of Conjugated Polyene
Compound (D) Blended in EVOH]
[0070] The amount of conjugated polyene compound (ID) in EVOH was
quantitatively determined in the following manner. In this method,
EVOH containing conjugated polyene compound (D) was pulverized and
sifted through a 100-mesh sieve to eliminate coarse particles. A 10
g portion of this powder was submitted to Soxhlet extraction for 48
hours with 100 ml of chloroform. The amount of conjugated polyene
compound in the extraction liquid was determined by high
performance liquid chromatography using calibration curves prepared
with the reference standard of each conjugated polyene
compound.
[NMR Analysis]
[0071] Various master batches containing EVAc (E) and S-EVOH (F),
prepared according to the manufacturing examples described below,
were individually dissolved in a mixed solvent of
o-dichlorobenzene/o-dichlorobenzene-d.sub.4=80/20 (volume ratio) at
a concentration of 5 mass %. Measurement was performed with
.sup.1H-NMR (500 MHz, measurement temperature=120.degree. C.,
accumulation number=1024 times, TMS, .delta. (ppm)). The signal
strength ratio between Ja and Jb was calculated by measuring the
area ratios of signal Jb at around 3.58 ppm (deriving from hydrogen
atoms bonded to the carbon atom to which hydroxyl group is bonded),
and signal Ja at around 5.05 ppm (deriving from hydrogen atoms
bonded to the carbon atom to which acetoxy group is bonded).
Manufacturing Example 1
[0072] (1) 2000 parts of EVOH having an ethylene content of 32 mol
%, having a degree of saponification of 99.8 mol %, and limiting
viscosity [q].sub.ph of 0.092 l/g as measured at 30.degree. C.
using a liquid mixture of water/phenol=15/85 (mass ratio) as a
solvent, were added to 18000 parts of a mixed solvent of
water/methanol=40/60 (mass ratio) and completely dissolved by
stirring for 6 hours at 60.degree. C. To this solution, 2 parts of
sorbic acid were added as a conjugated polyene compound (D) and
completely dissolved by stirring for 1 additional hour at
60.degree. C. to obtain EVOH solution containing sorbic acid. This
EVOH solution was continuously extruded into a coagulation bath of
water/methanol=5/95 (mass ratio) at 0.degree. C. through a nozzle
of 4 mm in diameter to coagulate EVOH in a stranded shape. This
strand was then introduced into a pelletizer to obtain porous EVOH
chips.
[0073] (2) The porous EVOH chips obtained in (1) above were
consecutively rinsed with 2000 parts of 0.1 mass % aqueous acetic
acid solution and then with 2000 parts of ion exchanged water at
20.degree. C. followed by immersion for 4 hours in 2000 parts of
0.092% aqueous boric acid solution at 20.degree. C. per 100 parts
of the chips. EVOH chips were dewatered and isolated from the
solution and dried for 4 hours in a hot-air drier at 80.degree. C.,
followed by drying for 16 hours at 100.degree. C. to obtain EVOH
chips. The obtained EVOH chips contained 0.11 part of boric acid
and 0.01 part of sorbic acid per 100 parts of EVOH.
[0074] The melt index of this EVOH was 1.6 g/10 minutes
(ASTM-D1238, measured at 190.degree. C., under a load of 2160 g).
This EVOH chip is called EVOH (B1).
Manufacturing Example 2
[0075] EVOH (B2) containing 0.05 part of .beta.-myrcene per 100
parts of EVOH was obtained in the same manner as in Manufacturing
Example 1 except for the use of 2 parts of p-myrcene instead of the
2 parts of sorbic acid in Manufacturing Example 1 (1) as the
conjugated polyene compound (D).
Manufacturing Example 3
[0076] EVOH (B3) was obtained in the same manner as in
Manufacturing Example 1 except that sorbic acid was not added to
EVOH water/methanol solution in Manufacturing Example 1 (1).
Manufacturing Example 4
[0077] EVOH (B4) containing 0.002 part of sorbic acid per 100 parts
of EVOH was obtained in the same manner as in Manufacturing Example
1 except for changing the amount of sorbic acid added to EVOH
water/methanol solution from 2 parts to 0.4 part in Manufacturing
Example 1 (1).
Manufacturing Example 5
[0078] EVOH (B5) containing 0.0032 part of sorbic acid per 100
parts of EVOH was obtained in the same manner as in Manufacturing
Example 1 except for changing the amount of sorbic acid added to
EVOH water/methanol solution from 2 parts to 0.65 part in
Manufacturing Example 1 (1).
Manufacturing Example 6
[0079] (1) Porous EVOH chips were obtained in the same manner as in
Manufacturing Example 1 except that EVOH having an ethylene content
of 32 mol % and a degree of saponification of 99.8 mol %, and an
limiting viscosity [.eta.].sub.ph of 0.112 l/g as measured at
30.degree. C. using a liquid mixture of water/phenol=15/85 (mass
ratio) as a solvent.
[0080] (2) The porous EVOH chips obtained in (1) above were
consecutively rinsed with 0.1 mass % aqueous acetic solution and
ion exchanged water in the same manner as in Manufacturing Example
1 (2), and then were dried in the same manner as in Manufacturing
Example 1 (2) without immersing in aqueous boric acid solution. In
this way, EVOH (B6) was obtained. The melt index of this EVOH
(ASTM-D1238, measured at 190.degree. C., under a load of 2160 g)
was 1.5 g/10 minutes.
Manufacturing Example 7
[0081] 40 parts of low density polyethylene {LDPE, melt index 1.5
g/10 minutes (ASTM-D1238, measured at 190.degree. C.), hereinafter
simply, "LDPE"}, 2 parts of calcium stearate which is a higher
fatty acid metal salt (C), 57.74 parts of EVAc (hereinafter simply,
"EVAc (E1)") with vinyl acetate units of 7.0 mol % and melt index
of 2.7 g/10 minutes (ASTM-D1238, measured at 190.degree. C., under
a load of 2160 g), and 2.26 parts of a saponified ethylene-vinyl
acetate copolymer (hereinafter, "S-EVOH (F1)") having an ethylene
content of 89 mol %, a degree of saponification of vinyl acetate
units of 97 mol % and melt index of 5.1 g/10 minutes (ASTM-D1238,
measured at 190.degree. C., under a load of 2160 g), were
dry-blended. The resulting mixture was pelletized after
melt-blending in a twin screw co-rotating extruder having a
diameter of 30 mm (TEX-30N (trade name), manufactured by Japan
Steel Works, Ltd.) at an extrusion temperature of 200.degree. C. to
obtain a master batch (MB1). According to the NMR analysis of this
master batch (MB1), the signal strength ratio (Ja:Jb) between the
signal Ja deriving from hydrogen atoms bonded to the carbon atom to
which acetoxy group is bonded, and the signal Jb deriving from
hydrogen atoms bonded to the carbon atom to which hydroxyl group is
bonded, was 94.0:6.0.
Manufacturing Example 8
[0082] In Manufacturing Example 7, 2 parts of
Mg.sub.6Al.sub.2(OH).sub.16CO.sub.3.4H.sub.2O which is a
hydrotalcite (G) were further added by dry-blending. The resulting
mixture was pelletized in the same manner as in Manufacturing
Example 7. Thus, a master batch (MB2) was obtained.
Manufacturing Example 9
[0083] The pelletizing was repeated in the same manner as in
Manufacturing Example 7 except that EVAc (E1) and S-EVOH (F1) were
not added in Manufacturing Example 7. Thus, the master batch (MB3)
was obtained.
Manufacturing Example 10
[0084] The pelletizing was repeated in the same manner as in
Manufacturing Example 7 except that calcium stearate was not added
in Manufacturing Example 7. Thus, the master batch (MB4) was
obtained.
Manufacturing Example 11
[0085] The pelletizing was repeated in the same manner as in
Manufacturing Example 7 except that 60 parts of EVAc (E1) were
used, instead of 57.74 parts of EVAc (E1) and 2.26 parts of S-EVOH
(F1) in Manufacturing Example 7. Thus, the master batch (M135) was
obtained.
Manufacturing Example 12
[0086] The pelletizing was repeated in the same manner as in
Manufacturing Example 7 except that 2 parts of magnesium stearate
were used as the higher fatty acid metal salt (C) instead of 2
parts of calcium stearate in Manufacturing Example 7. Thus, the
master batch (MB6) was obtained.
Manufacturing Example 13
[0087] The pelletizing was repeated in the same manner as in
Manufacturing Example 7 except that the added amount of EVAc (E1)
was changed from 57.74 parts to 13.47 parts, and that of S-EVOH
(F1) was changed from 2.26 parts to 0.53 part in Manufacturing
Example 7. Thus, the master batch (MB7) was obtained. According to
the NMR analysis of this master batch (MB7), the signal strength
ratio (Ja:Jb) between the signal Ja deriving from hydrogen atoms
bonded to the carbon atom to which acetoxy group is bonded, and the
signal Jb deriving from hydrogen atoms bonded to the carbon atom to
which hydroxyl group is bonded, was 94.0:6.0.
Manufacturing Example 14
[0088] The pelletizing was repeated in the same manner as in
Manufacturing Example 7 on the mixture obtained by dry-blending 2
parts of calcium stearate which is a higher fatty acid metal salt
(C), 57.74 parts of EVAc (E1) and 2.26 parts of S-EVOH (F1) in
Manufacturing Example 7. Thus, the master batch (MB8) was obtained.
According to the NMR analysis of this master batch (MB8), the
signal strength ratio (Ja:Jb) between the signal Ja deriving from
hydrogen atoms bonded to the carbon atom to which acetoxy group is
bonded, and the signal Jb deriving from hydrogen atoms bonded to
the carbon atom to which hydroxyl group is bonded, was
94.0:6.0.
Manufacturing Example 15
[0089] The pelletizing was repeated in the same manner as in
Manufacturing Example 7 except that 60 parts of S-EVOH (F1) were
used instead of 57.74 parts of EVAc (E1) and 2.26 parts of S-EVOH
(F1) in Manufacturing Example 7. Thus, the master batch (MB9) was
obtained.
Example 1
[0090] As polyolefin (A), polypropylene {melt index 5.4 g/10
minutes (ASTM-D1238, measured at 230.degree. C.), hereinafter "PP"}
was used. 88 parts of the PP, 10 parts of EVOH (B1), and 5.1 parts
of the master batch (MB1) were dry-blended to obtain a mixture. The
composition of this mixture was 88 parts of PP which is a
polyolefin (A), 2 parts of LDPE, 10 parts of EVOH (B), 0.1 part of
calcium stearate which is a higher fatty acid metal salt (C), 0.001
part of sorbic acid which is a conjugated polyene compound (D),
2.88 parts of EVAc (E1), and 0.12 part of S-EVOH (F1). Using a
single screw extruder having a diameter of 20 mm
(Laboplastmill--manufactured by Toyo Seiki, Co.) and a 300 mm wide
T-die extruder, a single layer film, 40 .mu.m thick, was
manufactured from this mixture. The film manufacturing temperature
was 190 to 230.degree. C. at the extruder, and 220.degree. C. at
the die. The screw rotation was 40 rpm, and the volume of discharge
was 0.95 kg/hour. About 50 m of the film was sampled 1 hour after
the mixture was put in the extruder hopper. On the center part of
the sampled film, a square, 10 cm by 10 cm, was drawn and the
number of EVOH aggregates, approximately 200 .mu.m or more in
diameter (the maximum diameter), in this square was counted using
the backlight of a table-top fluorescent lamp. This counting was
done at an interval of 20 cm, with a total of 100 positions along
the length of the sampled film. The average of EVOH aggregate count
per 100 cm.sup.2 was calculated to be 0.10 piece.
Example 2
[0091] The dry-blended mixture was obtained in the same manner as
in Example 1 except that 10 parts of EVOH (B2) containing p-myrcene
were used instead of 10 parts of EVOH (B1) containing sorbic acid
in Example 1. A single layer film was manufactured from this
mixture and then the EVOH aggregates in the obtained film were
counted in the same manner as in Example 1. The result was 0.12
piece per 100 cm.sup.2.
Example 3
[0092] The dry-blended mixture was obtained in the same manner as
in Example 1 except that 5.2 parts of the master batch (MB2)
containing a hydrotalcite (G) were dry-blended instead of 5.1 parts
of the master batch (MB1) in Example 1. A single layer film was
manufactured from this mixture and then the EVOH aggregates in the
obtained film were counted in the same manner as in Example 1. The
result was 0.04 piece per 100 cm.sup.2.
Comparative Example 1
[0093] In the process of Example 1, 90 parts of PP, and 10 parts of
EVOH (B3) not containing conjugated polyene compounds (D) were
dry-blended. A single layer film was manufactured from this mixture
and then the EVOH aggregates in the obtained film were counted in
the same manner as in Example 1. The result was 100 pieces or more
per 100 cm.sup.2.
Comparative Example 2
[0094] A single layer film was manufactured in the same manner as
in Example 1 except that 5.0 parts of the master batch (MB4) not
containing calcium stearate which is a higher fatty acid metal salt
(C) were used, instead of 5.1 parts of the master batch (MB1) in
Example 1. A single layer film was manufactured from this mixture
and then the EVOH aggregates in the obtained film were counted in
the same manner as in Example 1. The result was 7.51 pieces per 100
cm.sup.2.
Comparative Example 3
[0095] A single layer film was manufactured in the same manner as
in Example 1 except that 2.1 parts of the master batch (MB3) not
containing EVAc (E1) or S-EVOH (F1) were used instead of 5.1 parts
of the master batch (MB1) in Example 1. A single layer film was
manufactured from this mixture and then the EVOH aggregates in the
obtained film were counted in the same manner as in Example 1. The
result was 6.12 pieces per 100 cm.sup.2.
Comparative Example 4
[0096] A single layer film was manufactured in the same manner as
in Example 1 except that 5.1 parts of the master batch (MB5) not
containing S-EVOH (F1) were used instead of 5.1 parts of the master
batch (MB1) in Example 1. A single layer film was manufactured from
this mixture and then the EVOH aggregates in the obtained film were
counted in the same manner as in Example 1. The result was 4.33
pieces per 100 cm.sup.2.
Example 4
[0097] A single layer film was manufactured in the same manner as
in Example 1 except that 68 parts of PP; 30 parts of EVOH (B5); and
5.1 parts of the master batch (MB1) containing calcium stearate
which is a higher fatty acid metal salt (C), EVAc (E1), and S-EVOH
(F1); were dry-blended in Example 1. A single layer film was
manufactured from this mixture and then the EVOH aggregates in the
obtained film were counted in the same manner as in Example 1. The
result was 0.27 piece per 100 cm.sup.2.
Example 5
[0098] A single layer film was manufactured in the same manner as
in Example 1 except that 10 parts of EVOH (B6) not containing boric
acid were used, instead of 10 parts of EVOH (B1) in Example 1. A
single layer film was manufactured from this mixture and then the
EVOH aggregates in the obtained film were counted in the same
manner as in Example 1. The result was 0.45 piece per 100
cm.sup.2.
Example 6
[0099] A single layer film was manufactured in the same manner as
in Example 1 except that 5.1 parts of the master batch (MB6)
containing magnesium stearate were used, instead of 5.1 parts of
the master batch (MB1) which contain calcium stearate in Example 1.
A single layer film was manufactured from this mixture and then the
EVOH aggregates in the obtained film were counted in the same
manner as in Example 1. The result was 0.13 piece per 100
cm.sup.2.
Comparative Example 5
[0100] A single layer film was manufactured in the same manner as
in Example 1 except that 10 parts of EVOH (B3) not containing
conjugated polyene compounds (D) were used, instead of 10 parts of
EVOH (B1) in Example 1. A single layer film was manufactured from
this mixture and then the EVOH aggregates in the obtained film were
counted in the same manner as in Example 1. The result was 0.80
piece per 100 cm.sup.2.
Comparative Example 6
[0101] A single layer film was manufactured in the same manner as
in Example 1 except that 48 parts of PP, 50 parts of EVOH (B4), and
5.1 parts of the master batch (MB1) were dry-blended in Example 1.
A single layer film was manufactured from this mixture and then the
EVOH aggregates in the obtained film were counted in the same
manner as in Example 1. The result was 3.54 pieces per 100
cm.sup.2.
Comparative example 7
[0102] 88 parts of PP, 10 parts of EVOH (B1) containing conjugated
polyene compounds (D), and 5.1 parts of the master batch (MB1) were
dry-blended, and then further dry-blended with 19.9 parts of
calcium stearate. It was attempted to manufacture a single layer
film by using this mixture in the same manner as in Example 1.
However, calcium stearate in liquid form, which had separated from
the resins, seeped out of a T-die lip part and many holes were
formed on the film surface, and therefore counting of EVOH
aggregates was not possible.
Example 7
[0103] A single layer film was manufactured in the same manner as
in Example 1 except that 2.8 parts of the master batch (MB7) were
used, instead of 5.1 parts of the master batch (MB1) in Example 1.
A single layer film was manufactured from this mixture and then the
EVOH aggregates in the obtained film were counted in the same
manner as in Example 1. The result was 0.31 piece per 100
cm.sup.2.
Example 8
[0104] The process of Example 1 was repeated to prepare a dry blend
except that EVOH (B3) not containing conjugated polyene compound
(D) was used instead of 10 parts of EVOH (B1) in Example 1. To the
mixture thus obtained, sorbic acid which is a conjugated polyene
compound (D) was dry-blended by 0.001 part relative to 10 parts of
EVOH (B3). By using the obtained mixture, a single layer film was
manufactured in the same manner as in Example 1. The results showed
the EVOH aggregate count of 0.25 piece per 100 cm.sup.2.
Example 9
[0105] A single layer film was manufactured in the same manner as
in Example 1 except that 88 parts of high density polyethylene
{melt index 0.9 g/10 minutes (ASTM-D1238, measured at 190.degree.
C.) hereinafter, "HDPE"} were used instead of 88 parts of PP as
polyolefin (A) in Example 1. A single layer film was manufactured
from this mixture and then the EVOH aggregates in the obtained film
were counted in the same manner as in Example 1. The result was
0.18 piece per 100 cm.sup.2.
Comparative Example 8
[0106] In the process of Example 1, 88 parts of PP, 10 parts of
EVOH (B3) not containing conjugated polyene compound (D) and 5.1
parts of the master batch (MB1) were dry-blended. To the mixture
thus obtained, 5 parts of sorbic acid which is a conjugated polyene
compound (D) were added and further dry-blended to prepare a
uniform blend. By using this mixture, a single layer film was
manufactured in the same manner as in Example 1. The results showed
the EVOH aggregate count of 100 pieces or more per 100
cm.sup.2.
Comparative Example 9
[0107] A single layer film was manufactured in the same manner as
in Example 9 except that 90 parts of HDPE were used and the master
batch (MB1) was not added in Example 9. A single layer film was
manufactured from this mixture and then the EVOH aggregates in the
obtained film were counted in the same manner as in Example 1. The
result was 4.56 pieces per 100 cm.sup.2.
Example 10
[0108] The dry-blended mixture was obtained in the same manner as
in Example 1 except that 90 parts of PP and 3.1 parts of the master
batch (MB8) were used, instead of 88 parts of PP and 5.1 parts of
the master batch (MB1) in Example 1. A single layer film was
manufactured from this mixture and then the EVOH aggregates in the
obtained film were counted in the same manner as in Example 1. The
result was 0.11 piece per 100 cm.sup.2.
Comparative Example 10
[0109] A single layer film was manufactured in the same manner as
in Example 1 except that 5.1 parts of the master batch (MB9) not
containing EVAc (E1) were used, instead of 5.1 parts of the master
batch (MB1) in Example 1. A single layer film was manufactured from
this mixture and then the EVOH aggregates in the obtained film were
counted in the same manner as in Example 1. The result was 0.87
piece per 100 cm.sup.2.
Example 11
[0110] Manufacturing testing of co-extrusion film including the
resin composition layers of the present invention was performed by
using the following four types of 7-layer co-extrusion cast film
manufacturing equipment.
Extruder (1): single screw, screw diameter 65 mm, L/D=22, for outer
layer polyolefin Extruder (2): single screw, screw diameter 40 mm,
L/D=26, for resin composition of this present invention Extruder
(3): single screw, screw diameter 40 mm, L/D=22, for adhesive
resins Extruder (4): single screw, screw diameter 40 mm, L/D=26,
for EVOH
[0111] Co-extrusion film manufacturing was performed by feeding PP
into Extruder (1), a mixture of 88 parts of PP, 10 parts of EVOH
(B1), and 5.1 parts of the master batch (MB1) prepared by
dry-blending in the same manner as in Example 1, into Extruder (2),
a modified polypropylene adhesive resin modified with maleic acid
anhydride (ADMER QF-500 (tradename), manufactured by Mitsui
Chemical, Inc.) into Extruder (3), and EVOH (B1) into Extruder (4),
respectively. The extrusion temperature was 200 to 240.degree. C.
for Extruder (1), 160 to 220.degree. C. for Extruder (2), 160 to
230.degree. C. for Extruder (3), 170 to 210.degree. C. for Extruder
(4), and 220.degree. C. for feed block and die. The objective for
the manufactured multilayer film composition and the thickness was:
PP/resin composition of the present invention/adhesive
resin/EVOH/adhesive resin/resin composition of the present
invention/PP=30/15/2.5/5/2.5/15/30 .mu.m, a total of 100 .mu.m in
thickness made of four types and seven layers.
[0112] According to the observation of the appearance of the film
sampling of the multilayer film after 2 hours following the
initiation of the film manufacturing, it was concluded that the
obtained multilayer film does not present any problem for practical
application, with hardly any deteriorated appearance attributable
to EVOH aggregation.
Comparative Example 11
[0113] A multilayer film was obtained in the same manner as in
Example 11 except that the mixture used for feeding the Extruder
(2) in Example 11 was replaced by the mixture used in Comparative
Example 1 prepared by dry-blending 90 parts of PP and 10 parts of
EVOH (B3). The obtained multilayer film clearly showed a poor
appearance due to EVOH aggregates at a level unsuitable for
practical application.
Comparative Example 12
[0114] A multilayer film was obtained in the same manner as in
Example 11 except that the mixture used for feeding the Extruder
(2) in Example 11 was replaced by the mixture used in Comparative
Example 5 prepared by dry-blending 88 parts of PP, 10 parts of EVOH
(B3) not containing conjugated polyene compounds (D); and 5.1 parts
of the master batch (MB1) containing calcium stearate which is a
higher fatty acid metal salt (C), EVAc (E1), and S-EVOH (F1).
Although the appearance of the obtained multilayer film was better
than that of the multilayer film of Comparative Example 11, it
still showed some poor appearance due to EVOH aggregates at a level
unsuitable for practical application.
Comparative Example 13
[0115] A multilayer film was obtained in the same manner as in
Example 11 except that the mixture used for feeding the Extruder
(2) in Example 11 was replaced by the mixture used in Comparative
Example 3 prepared by dry-blending 88 parts of PP, 10 parts of EVOH
(B1), and 2.1 parts of the master batch (MB3) not containing EVAc
(E1) or S-EVOH (F1). Although the appearance of the obtained
multilayer film was better than that of the multilayer film of
Comparative Example 11, it still showed some poor appearance due to
EVOH aggregates at a level unsuitable for practical
application.
Comparative Example 14
[0116] A multilayer film was obtained in the same manner as in
Example 11 except that the mixture used for feeding the Extruder
(2) in Example 11 was replaced by the mixture used in Comparative
Example 2 prepared by dry-blending 88 parts of PP, 10 parts of EVOH
(B1), and 5.0 parts of the master batch (MB4) not containing higher
fatty acid metal salts (C). Although the appearance of the obtained
multilayer film was better than that of the multilayer film of
Comparative Example 11, it still showed some poor appearance due to
EVOH aggregates at a level unsuitable for practical
application.
Example 12
[0117] A multilayer film was obtained in the same manner as in
Example 11 except that the mixture used for feeding the Extruder
(2) in Example 11 was replaced by the mixture used in Example 3
prepared by dry-blending 88 parts of PP, 10 parts of EVOH (B1), and
5.2 parts of the master batch (MB2) containing a hydrotalcite (G).
The appearance of the obtained multilayer film was even better than
that of the multilayer film of Example 11, with no poor appearance
due to EVOH aggregates.
[0118] The results of each Example and Comparative Example are
summarized in Table 1 and Table 2.
TABLE-US-00001 TABLE 1 Polyolefin (A) EVOH (B) Higher fatty acid
metal salt (C) Type Amount Type Amount Type Amount Type
Amount.sup.1) EX. 1 PP 88 LDPE 2 EVOH(B1) 10 Calcium stearate 0.1
EX. 2 PP 88 LDPE 2 EVOH(B2) 10 Calcium stearate 0.1 EX. 3 PP 88
LDPE 2 EVOH(B1) 10 Calcium stearate 0.1 EX. 4 PP 68 LDPE 2 EVOH(B5)
30 Calcium stearate 0.1 EX. 5 PP 88 LDPE 2 EVOH(B6) 10 Calcium
stearate 0.1 EX. 6 PP 88 LDPE 2 EVOH(B1) 10 Magnesium stearate 0.1
EX. 7 PP 88 LDPE 2 EVOH(B1) 10 Calcium stearate 0.1 EX. 8 PP 88
LDPE 2 EVOH(B3) 10 Calcium stearate 0.1 EX. 9 HDPE 88 LDPE 2
EVOH(B1) 10 Calcium stearate 0.1 EX. 10 PP 90 EVOH(B1) 10 Calcium
stearate 0.1 Comparative EX. 1 PP 90 EVOH(B3) 10 -- -- Comparative
EX. 2 PP 88 LDPE 2 EVOH(B1) 10 -- -- Comparative EX. 3 PP 88 LDPE 2
EVOH(B1) 10 Calcium stearate 0.1 Comparative EX. 4 PP 88 LDPE 2
EVOH(B1) 10 Calcium stearate 0.1 Comparative EX. 5 PP 88 LDPE 2
EVOH(B3) 10 Calcium stearate 0.1 Comparative EX. 6 PP 48 LDPE 2
EVOH(B4) 50 Calcium stearate 0.1 Comparative EX. 7 PP 88 LDPE 2
EVOH(B1) 10 Calcium stearate 20 Comparative EX. 8 PP 88 LDPE 2
EVOH(B3) 10 Calcium stearate 0.1 Comparative EX. 9 HDPE 90 EVOH(B1)
10 -- -- Comparative EX. 10 PP 88 LDPE 2 EVOH(B1) 10 Calcium
stearate 0.1 NMR EVOH Conjugated polyene EVAc S-EVOH Hydrotalcite
strength aggregate compound (D) (E) (F) (G) ratio count Type
Amount.sup.1) Amount.sup.1) Amount.sup.1) Amount.sup.1) Ja:Jb (per
100 cm.sup.2) EX. 1 sorbic acid 0.001 2.88 0.12 94.0:6.0 0.10 EX. 2
.beta.-myrcene 0.005 2.88 0.12 94.0:6.0 0.12 EX. 3 sorbic acid
0.001 2.88 0.12 0.01.sup.2) 94.0:6.0 0.04 EX. 4 sorbic acid 0.00096
2.88 0.12 94.0:6.0 0.27 EX. 5 sorbic acid 0.001 2.88 0.12 94.0:6.0
0.45 EX. 6 sorbic acid 0.001 2.88 0.12 94.0:6.0 0.13 EX. 7 sorbic
acid 0.001 0.672 0.028 94.0:6.0 0.31 EX. 8 sorbic acid 0.001 2.88
0.12 94.0:6.0 0.25 EX. 9 sorbic acid 0.001 2.88 0.12 94.0:6.0 0.18
EX. 10 sorbic acid 0.001 2.88 0.12 94.0:6.0 0.11 Comparative EX. 1
-- -- -- -- -- >100 Comparative EX. 2 sorbic acid 0.001 2.88
0.12 94.0:6.0 7.51 Comparative EX. 3 sorbic acid 0.001 -- -- --
6.12 Comparative EX. 4 sorbic acid 0.001 3 -- 100:0 4.33
Comparative EX. 5 -- -- 2.88 0.12 94.0:6.0 0.80 Comparative EX. 6
sorbic acid 0.001 2.88 0.12 94.0:6.0 3.54 Comparative EX. 7 sorbic
acid 0.001 2.88 0.12 94.0:6.0 --.sup.3) Comparative EX. 8 sorbic
acid 5 2.88 0.12 94.0:6.0 >100 Comparative EX. 9 sorbic acid
0.001 -- -- -- 4.56 Comparative EX. 10 sorbic acid 0.001 -- 3
3.0:97.0 0.87 .sup.1)Parts by mass per 100 parts by mass of the
total of the polyolefin (A) and the EVOH (B) .sup.2)Hydrotalcite:
Mg.sub.6Al.sub.2(OH).sub.16CO.sub.3.cndot.4H.sub.2O .sup.3)Film
manufacture was impossible due to foaming
TABLE-US-00002 TABLE 2 Polyoletin (A) EVOH (B) Higher fatty acid
metal salt (C) Type Amount Type Amount Type Amount Type
Amount.sup.1) EX. 11 PP 80 LDPE 2 EVOH(B1) 10 Calcium 0.1 stearate
EX. 12 PP 80 LDPE 2 EVOH(B1) 10 Calcium 0.1 stearate Comparative
EX. 11 PP 90 EVOH(B3) 10 -- -- Comparative EX. 12 PP 88 LDPE 2
EVOH(B3) 10 Calcium 0.1 stearate Comparative EX. 13 PP 88 LDPE 2
EVOH(B1) 10 Calcium 0.1 stearate Comparative EX. 14 PP 88 LDPE 2
EVOH(B1) 10 -- -- NMR Conjugated polyene EVAc S-EVOH Hydrotalcite
strength compound (D) (E) (F) (G) ratio Film surface Type
Amount.sup.1) Amount.sup.1) Amount.sup.1) Amount.sup.1) Ja:Jb
appearance.sup.3) EX. 11 sorbic 0.001 2.88 0.12 94.0:6.0 B acid EX.
12 sorbic 0.001 2.88 0.12 0.1.sup.2) 94.0:6.0 A acid Comparative
EX. 11 -- -- -- -- D Comparative EX. 12 -- -- 2.88 0.12 94.0:6.0 C
Comparative EX. 13 sorbic 0.001 -- -- C acid Comparative EX. 14
sorbic 0.001 2.88 0.12 94.0:6.0 C acid .sup.1)Parts by mass per 100
parts by mass of the total of the polyolefin (A) and the EVOH (B)
.sup.2)Hydrotalcite: Mg.sub.6Al.sub.2(OH).sub.16CO.sub.1.cndot.4H2O
.sup.3)A: No appearance anomalies were found B: Appearance
anomalies were substantially not found, hence practically
acceptable. C: Some appearance anomalies were found, hence
practically problematic. D: Appearance anomalies were clearly
found, hence practically problematic.
[0119] The present invention relates to a resin composition
comprising: polyolefin (A); EVOH (B); higher fatty acid metal salt
(C) having 8 to 22 carbon atoms; conjugated polyene compound (D)
having a boiling point of 20.degree. C. or higher; EVAc (E); and
S-EVOH (F), wherein the mass ratio (A:B) of polyolefin (A) and EVOH
(B) is 60:40 to 99.9:0.1, the amount of higher fatty acid metal
salts (C) is in the range of 0.0001 to 10 parts by mass per 100
parts by mass of the total of polyolefin (A) and EVOH (B), the
amount of conjugated polyene compound (D) is in the range of
0.000001 to 1 part by mass per 100 parts by mass of the total of
polyolefin (A) and EVOH (B), and the total amount of EVAc (E) and
saponified ethylene-vinyl acetate copolymer (F) is 0.3 part by mass
or more per 100 parts by mass of the total of polyolefin (A) and
EVOH (B). By using this composition, a poor appearance caused by
the EVOH aggregation and flow anomalies attributable to the
aggregation can be prevented, and molded articles having an
excellent appearance can be obtained.
* * * * *