U.S. patent application number 13/964428 was filed with the patent office on 2013-12-12 for epoxy-group-containing copolymer, epoxy (meth)acrylate copolymer using the same, and their production processes.
This patent application is currently assigned to SHOWA DENKO K.K.. The applicant listed for this patent is SHOWA DENKO K.K.. Invention is credited to Toshio FUJITA, Masanao HARA, Kazuhiko OOGA, Hiroshi UCHIDA.
Application Number | 20130331531 13/964428 |
Document ID | / |
Family ID | 41663797 |
Filed Date | 2013-12-12 |
United States Patent
Application |
20130331531 |
Kind Code |
A1 |
UCHIDA; Hiroshi ; et
al. |
December 12, 2013 |
EPOXY-GROUP-CONTAINING COPOLYMER, EPOXY (METH)ACRYLATE COPOLYMER
USING THE SAME, AND THEIR PRODUCTION PROCESSES
Abstract
According to the present invention, a novel epoxy
group-containing copolymer, including a production process thereof,
and an epoxy (meth)acrylate copolymer starting from the epoxy
group-containing copolymer, including a production process thereof
are provided. The epoxy group-containing copolymer of the present
invention contains a specific epoxy group-containing repeating unit
and an olefin-based repeating unit. A novel epoxy (meth)acrylate
copolymer of the present invention is produced by reacting the
epoxy group-containing copolymer with (meth)acrylic acid.
Inventors: |
UCHIDA; Hiroshi; (Tokyo,
JP) ; OOGA; Kazuhiko; (Tokyo, JP) ; FUJITA;
Toshio; (Tokyo, JP) ; HARA; Masanao; (Tokyo,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SHOWA DENKO K.K. |
Minato-ku |
|
JP |
|
|
Assignee: |
SHOWA DENKO K.K.
MINATO-KU
JP
|
Family ID: |
41663797 |
Appl. No.: |
13/964428 |
Filed: |
August 12, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
13057425 |
Feb 3, 2011 |
8541508 |
|
|
PCT/JP2009/064051 |
Aug 7, 2009 |
|
|
|
13964428 |
|
|
|
|
Current U.S.
Class: |
526/268 |
Current CPC
Class: |
C08F 224/00 20130101;
C08F 8/14 20130101; C08F 8/14 20130101; H01B 3/40 20130101; C08F
220/32 20130101; C08F 2810/20 20130101; C08F 220/14 20130101; C08F
218/02 20130101 |
Class at
Publication: |
526/268 |
International
Class: |
H01B 3/40 20060101
H01B003/40 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 8, 2008 |
JP |
2008-206114 |
Nov 28, 2008 |
JP |
2008-305179 |
Claims
1. An epoxy group-containing copolymer comprising at least one of
repeating units represented by the following formulae (a), (b) and
(c): ##STR00026## wherein each of R.sup.1 to R.sup.11 is a hydrogen
atom or a methyl group, and R.sup.12 is a hydrogen atom, a methyl
group or a phenyl group, and a repeating unit represented by the
following formula (d): ##STR00027## wherein R.sup.14 is a hydrogen
atom or a methyl group, and R.sup.15 is a hydrogen atom or a
saturated or unsaturated hydrocarbon group having a carbon number
of 24 or less.
2. The epoxy group-containing copolymer as claimed in claim 1,
wherein the epoxy equivalent of said copolymer is from 190 to 3,000
g/eq.
3. The epoxy group-containing copolymer as claimed in claim 1,
wherein the number average molecular weight of said copolymer is
from 400 to 10,000.
4. The epoxy group-containing copolymer as claimed in claim 1,
wherein the total content of the repeating units represented by
formulae (a), (b) and (c) in said copolymer is from 10 to 90 mol %,
the content of the repeating unit represented by formula (d) is
from 5 to 90 mol %, and the total of the total content of the
repeating units represented by formulae (a), (b) and (c), and the
content of the repeating unit represented by formula (d) is 100 mol
% or less.
5. The epoxy group-containing copolymer as claimed in claim 1,
wherein the repeating unit represented by formula (a) is at least
one of repeating units represented by the following formulae (a1)
to (a6) and the repeating unit represented by formula (c) is at
least one of repeating units represented by the following formulae
(c1) and (c2): ##STR00028## ##STR00029##
6. The epoxy group-containing copolymer as claimed in claim 1,
wherein the repeating unit represented by formula (d) is derived
from an ethylene and/or an unsaturated hydrocarbon having a carbon
number of 8 or more.
7. The epoxy group-containing copolymer as claimed in claim 1,
wherein the repeating unit represented by formula (d) is derived
from ethylene, propylene, isobutene, 1-butene, 3-methylbutene-1,
1-pentene, 2-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,
1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, 4-vinylcyclohexene, 5-vinylnorbornene,
limonene or allylbenzene.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This is a divisional of application Ser. No. 13/057,425
filed Feb. 3, 2011, which is the National Stage of
PCT/JP2009/064051 filed Aug. 7, 2009 (which claims benefit of
Japanese Patent Application No. JP 2008-206114 filed Aug. 8, 2008,
and Japanese Patent Application No. JP 2008-305179 filed Nov. 28,
2008), the disclosures of which are hereby incorporated by
reference.
TECHNICAL FIELD
[0002] The present invention relates to a novel epoxy
group-containing copolymer excellent in electrical insulation,
promising utilization in the fields of, for example, an electrical
insulating material, such as a solder resist and an interlayer
insulating film, an encapsulant of IC and VLSI, and a laminated
sheet, and a production process thereof. The present invention also
relates to an epoxy (meth)acrylate copolymer obtained by reacting
the epoxy group-containing copolymer above with (meth)acrylic acid,
which is free from a low volatile monomer, such as styrene, and
curable by either light or heat, promising utilization in the
fields of, for example, an electrical insulating material, such as
a solder resist and an interlayer insulating film, an encapsulant
of IC and VLSI, and a laminated sheet, and which has not only
well-balanced flexibility and toughness but also excellent low
dielectric characteristics, adherence, water resistance, heat
resistance, chemical resistance, electrical insulation and the
like, and a production process thereof.
BACKGROUND ART
[0003] Recently, significant progress has been made in the polymer
industry, which has resulted in use of varied and diverse polymer
materials over a wide range. In particular, with the enhancement in
function and performance of industrial products, development of a
more
excellent polymer material is proceeding.
[0004] Among such materials, an epoxy resin has wide industrial
applications as a thermosetting resin or other reactive resins and
has been studied and developed from various aspects. The epoxy
resin that is most widely used in the industry at present is a
bisphenol A-type epoxy resin produced by the reaction of bisphenol
A and epichlorohydrin.
[0005] This resin includes a wide range of liquid to solid
products, and is also excellent in reactivity, chemical resistance,
toughness, adhesion, heat resistance and the like, and therefore it
finds extensive uses, for example, in civil engineering,
architecture, coatings and adhesives. However, since the bisphenol
A-type epoxy resin is obtained by the reaction of bisphenol A and
epichlorohydrin, tens of ppm to 100 ppm of chlorine is contained in
the resin, and this brings about a problem, such as impairment of
electrical characteristics of an electric component. Furthermore,
with the recent reduction in size and weight of an electrical
component, a flexible wiring board becomes increasingly popular,
and flexibility is also required of the insulating resin itself so
as to reduce the thickness and weight. Accordingly, an epoxy resin
free from chlorine and balanced in the electrical characteristics,
heat resistance and flexibility is demanded.
[0006] An alicyclic epoxy resin is known as a chlorine-free resin,
and a compound represented by the following formula (e) or (f):
##STR00001##
is industrially produced and used as a raw material of the
alicyclic epoxy resin. Such a material has a high glass transition
temperature and excellent heat resistance but is disadvantageously
low in flexibility.
[0007] As for other epoxy resins containing reduced residual
halogen, there have been proposed, for example, an epoxy resin
obtained by ring-opening polymerizing 4-vinyl-cyclohexane oxide and
then epoxidizing the vinyl group (see, Patent Document 1 below), a
resin produced by epoxidizing a compound obtained through
alternating copolymerization of 4-vinyl-cyclohexane oxide and an
acid anhydride (see, Patent Document 2 below), an epoxy resin
composition obtained by polymerizing a methacrylic acid ester of
epoxycyclohexanemethanol with another methacrylic or acrylic acid
ester (see, Patent Document 3 below), and an epoxy resin
composition obtained by polymerizing allyl
3,4-epoxycyclohexane-1-carboxylate with an allyl ester, a vinyl
ester, a vinyl ether, a (meth)acrylic acid ester or the like (see,
Patent Document 4 below). However, still higher performance is
demanded in electrical characteristics, heat resistance and
flexibility.
[0008] On the other hand, a thermosetting resin, such as
unsaturated polyester resins and epoxy (meth)acrylate resins, is
being widely used, for example, as a base material of FRP
(fiber-reinforced plastic) for an electronic material, a building
material, a transportation device, industrial equipment and
materials and the like, or for a casting mold, a coating material,
an adhesive, a resin concrete, a decorative sheet and the like.
[0009] The unsaturated polyester resin is a viscous liquid resin
generally obtained by polycondensing an alcohol component composed
of a polyhydric alcohol and an acid component composed of
.alpha.,.beta.-unsaturated polyvalent carboxylic acids and
saturated polyvalent carboxylic acids or aromatic polyvalent
carboxylic acids, and blending the resulting unsaturated polyester
with a radical polymerizable monomer, such as styrene. By changing
the kinds and amounts of the polyhydric alcohol as well as the acid
component composed of .alpha.,.beta.-unsaturated polyvalent
carboxylic acids and saturated polyvalent carboxylic acids or
aromatic polyvalent carboxylic acids used for the production of an
unsaturated polyester, an unsaturated polyester resin composition
having physical properties suitable for various intended uses or
being moldable by a molding method suitable for the intended use
can be produced.
[0010] An epoxy (meth)acrylate resin is derived from a polyhydric
phenol-type epoxy resin, such as bisphenol-type epoxy resins and
novolak-type epoxy resins, and (meth)acrylic acid, and is known as
a resin with excellent moldability in view of curability,
workability and the like, and usually, such a resin is also widely
used by blending a radical polymerizable crosslinking agent, such
as styrene.
[0011] However, this resin system contains approximately from 30 to
60 mass % of styrene, which is a radical polymerizable monomer.
Thus, in an open-mold molding method, such as hand lay-up molding
and spray-up molding, styrene contained in the resin often
volatilizes during FRP shaping to worsen the molding working
environment. In recent years, for example, the law of PRTR
(Pollutant Release and Transfer Register) has been implemented, and
regulations on discharge of chemical substances are tightened.
Under such conditions, styrene contained in the resin above comes
under a substance to be regulated. It is required of course in
open-mold molding but also in other molding methods to reduce the
amount of volatilized styrene so as to meet the regulations or to
improve the molding working environment.
[0012] As for a method for reducing the content of a styrene
monomer, there is a method of keeping low the molecular weight of a
thermosetting resin, such as unsaturated polyester resins and epoxy
acrylate resins, to lower the viscosity and thereby decrease the
blending amount of the monomer (for example, decrease the amount of
styrene).
[0013] In the case of an unsaturated polyester resin, the method
for reducing the molecular weight generally includes a method of
controlling the reaction to keep the molecular weight low, a method
of capping the molecular terminal by modification with
dicyclopentadiene to keep the molecular weight low (see, for
example, Patent Documents 5 and 6 below), and a method of replacing
a part of the polyhydric alcohol with a monoalcohol to cap the
molecular terminal and thereby keep the molecular weight low (see,
for example, Patent Document 7 below). In these methods, the
absolute amount of styrene contained in the unsaturated polyester
resin can be reduced to about 30 mass %, and therefore instability
in the effect of suppressing styrene and decrease of the secondary
adhesion, which are observed when utilizing a paraffin wax-based
additive, do not occur, and therefore a stable effect of
suppressing styrene can be obtained. Furthermore, since reduction
in the viscosity can also be achieved by these methods, the molding
workability, such as injection and filling in the RTM molding, can
be improved and in the case of using the resin for a resin
concrete, the amount of filler can be increased without impairing
the moldability, such as fluidity and filling properties.
[0014] However, in the method of merely controlling the molecular
weight, reduction in the molecular weight of the unsaturated
polyester resin involves reduction in the mechanical properties of
the resulting cured product, such as strength and elongation
percentage, and moreover, the terminal group (hydroxyl group,
carboxyl group) of the polyester increases, thereby resulting in
the water resistance of the resulting cured product being greatly
deteriorated.
[0015] In addition, in the case of a dicyclopentadiene-modified
unsaturated polyester resin in which the molecular terminal is
capped by using dicyclopentadiene so as to reduce the amount of a
hydrophilic terminal group, the mechanical properties of the
resulting cured product, such as strength and elongation
percentage, are often impaired due to the chemical structure and
decreased molecular weight of the dicyclopentadiene-modified
unsaturated polyester resin.
RELATED ART
Patent Document
[0016] Patent Document 1: Kokai (Japanese Unexamined Patent
Publication) No. 60-166675 [0017] Patent Document 2: Kokai No.
06-41275 [0018] Patent Document 3: Kokai No. 08-291214 [0019]
Patent Document 4: Kokai No. 2007-204642 [0020] Patent Document 5:
Kokai No. 54-159492 [0021] Patent Document 6: Kokai No. 53-092888
[0022] Patent Document 7: Kokai No. 52-003686
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0023] Each of the above-described conventional techniques has
achieved results but is still insufficient in some aspects. For
example, cyclohexene oxides having a low molecular weight are toxic
on a worker's skin. In addition, both of the compounds represented
by formulae (e) and (f) have low viscosity, and therefore a molding
system for a solid epoxy resin, such as transfer molding, cannot be
applied.
[0024] Furthermore, in Patent Documents 1 and 2,
4-vinyl-epoxycyclohexane is polymerized by ring-opening
polymerizing the epoxy group thereof, and in the next step, formed
into an epoxy resin by using a peracid, but it is difficult for the
epoxidization after polymerization to convert all double bonds into
an epoxy group industrially in a high yield. In Patent Document 3,
it is difficult to control the molecular weight of the polymer by
radical polymerization of an acrylic acid ester or methacrylic acid
ester of epoxycyclohexane, and if the molecular weight becomes
excessively large, this may cause a problem in the compatibility,
solubility and the like.
[0025] In Patent Document 4, it is easy to control the molecular
weight because of polymerization of an allyl group, but the
copolymer with an acrylic acid ester or an allyl ester or vinyl
ester is not necessarily sufficient in the electrical
insulation.
[0026] Accordingly, an object of the present invention is to
provide a novel epoxy-containing copolymer being excellent in the
electrical insulation and having controllable physical properties,
such as flexibility and adherence.
[0027] Taking into consideration the problems in the
above-described conventional techniques related to a thermosetting
resin, such as unsaturated polyester resins and epoxy
(meth)acrylate resins, another object of the present invention is
to provide an epoxy (meth)acrylate copolymer ensuring that curing
by either light through irradiation of an active energy ray or heat
is possible even without containing a low volatile monomer, such as
styrene, and in addition to good balance between flexibility and
toughness, properties, such as low dielectric characteristics,
water resistance, heat resistance, chemical resistance, electrical
insulation and good moldability, can be controlled; and a
production process thereof.
Means to Solve the Problems
[0028] The present inventors have intensively studied the objects
above and have performed a number of experiments, and as a result,
they have succeeded in unexpectedly obtaining an epoxy
group-containing polymer having high hydrophobicity and good
electrical insulation, and a low halogen concentration by
performing radical copolymerization of a base compound having an
allyl group and/or a vinyl group in combination with an alicyclic
epoxy group epoxidized through hydrogen peroxide oxidation or
peracetic acid oxidation but not by a halohydrin method with a
terminal olefin compound composed only of a hydrocarbon, and
succeeded in obtaining a novel epoxy group-containing polymer
having controllable physical properties, such as flexibility and
adherence, required in usage, such as a solder resist of a flexible
print board, by performing copolymerization with another compound
containing an ethylenically unsaturated bond. The present invention
has been accomplished based on these successes.
[0029] Furthermore, the present inventors have succeeded in
obtaining an epoxy group-containing polymer having a low halogen
concentration by performing radical copolymerization of a base
compound having both an alicyclic epoxy group epoxidized through
hydrogen peroxide oxidation or peracetic acid oxidation but not by
a halohydrin method and an allyl group with a terminal olefin
compound composed only of a hydrocarbon, and succeeded in obtaining
a novel epoxy (meth)acrylate copolymer having controllable physical
properties, such as flexibility and adherence, and being curable by
either light through irradiation of an active energy ray or heat,
which is useful in usage, such as a solder resist of a flexible
print board, by reacting the epoxy group-containing copolymer above
with (meth)acrylic acid. The present invention has been
accomplished based on these successes.
[0030] In other words, the present invention relates to an
epoxy-containing copolymer obtained, as described below, by radical
copolymerization of a compound having an alicylcic epoxy group in
combination with an allyl group and/or a vinyl group with a
terminal olefin composed only of a hydrocarbon, and a production
process thereof. Furthermore, the present invention relates to an
epoxy (meth)acrylate copolymer obtained, as described below, by the
reaction between an epoxy group-containing copolymer, which is
obtained by radical copolymerization of a compound having both an
alicyclic epoxy group and an allyl group with a terminal olefin
composed only of a hydrocarbon, and (meth)acrylic acid, and a
production process thereof.
[0031] Specifically, the present invention includes the following
[1] to [17].
[0032] [1] An epoxy group-containing copolymer comprising at least
one of repeating units represented by the following formulae (a),
(b) and (c):
##STR00002##
wherein each of R.sup.1 to R.sup.11 is a hydrogen atom or a methyl
group, and R.sup.12 is a hydrogen atom, a methyl group or a phenyl
group, and
[0033] a repeating unit represented by the following formula
(d):
##STR00003##
wherein R.sup.14 is a hydrogen atom or a methyl group, and R.sup.15
is a hydrogen atom or a saturated or unsaturated hydrocarbon group
having a carbon number of 24 or less.
[0034] [2] The epoxy group-containing copolymer as described in [1]
above, wherein the epoxy equivalent of the copolymer is from 190 to
3,000 g/eq.
[0035] [3] The epoxy group-containing copolymer as described in [1]
or [2] above, wherein the number average molecular weight of the
copolymer is from 400 to 10,000.
[0036] [4] The epoxy group-containing copolymer as described in any
one of [1] to [3] above, wherein the total content of the repeating
units represented by formulae (a), (b) and (c) in the copolymer is
from 10 to 90 mol %, the content of the repeating unit represented
by formula (d) is from 5 to 90 mol %, and the total of the total
content of the repeating units represented by formulae (a), (b) and
(c), and the content of the repeating unit represented by formula
(d) is 100 mol % or less.
[0037] [5] The epoxy group-containing copolymer as described in any
one of [1] to [4] above, wherein the repeating unit represented by
formula (a) is at least one of repeating units represented by the
following formulae (a1) to (a6) and the repeating unit represented
by formula (c) is at least one of repeating units represented by
the following formulae (c1) and (c2):
##STR00004## ##STR00005##
[0038] [6] The epoxy group-containing copolymer as described in any
one of [1] to [5] above, wherein the repeating unit represented by
formula (d) is derived from an ethylene and/or an unsaturated
hydrocarbon having a carbon number of 8 or more.
[0039] [7] A process for producing the epoxy group-containing
copolymer described in any one of [1] to [6] above, comprising
radically-copolymerizing
[0040] at least one of monomers containing an epoxy group and an
allyl or vinyl group, represented by the following formulae (1),
(2) and (3):
##STR00006##
wherein each of R.sup.1 to R.sup.11 is a hydrogen atom or a methyl
group, and R.sup.12 is a hydrogen atom, a methyl group or a phenyl
group, with
[0041] an olefin represented by the following formula (4):
##STR00007##
wherein R.sup.14 is a hydrogen atom or a methyl group, and R.sup.15
is a hydrogen atom or a saturated or unsaturated hydrocarbon group
having a carbon number of 24 or less.
[0042] [8] A process for producing the epoxy group-containing
copolymer described in any one of [1] to [6] above, comprising
radically-copolymerizing
[0043] at least one of monomers represented by the following
formula (5):
##STR00008##
with
[0044] at least one of ethylene, 4-methyl-1-pentene, 1-octene,
1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene,
4-vinylcyclohexene and limonene.
[0045] [9] A process for producing the epoxy group-containing
copolymer described in any one of [1] to [6] above, comprising
radically-copolymerizing
[0046] at least one of allyl 3,4-epoxycyclohexane-1-carboxylate,
allyl 3,4-epoxy-1-methylcyclohexanecarboxylate and allyl
3,4-epoxy-6-phenylcyclohexanecarboxylate, with
[0047] at least one of 4-methyl-1-pentene, 1-decene, 1-dodecene,
1-tetradecene, 1-hexadecene and 1-octadecene.
[0048] [10] The process for producing an epoxy group-containing
copolymer as described in any one of [7] to [9] above, wherein low
molecular components containing monomers are distilled off by using
a thin-film evaporation apparatus or a molecular distillation
apparatus after the copolymerization.
[0049] [11] An epoxy (meth)acrylate copolymer comprising
[0050] at least one of repeating units represented by the following
formulae (a1'), (a2'), (b1) and (b2):
##STR00009##
wherein each of R.sup.1 to R.sup.9 and R.sup.13 is a hydrogen atom
or a methyl group, and R.sup.12 is a hydrogen atom, a methyl group
or a phenyl group, and a repeating unit represented by the
following formula (d):
##STR00010##
wherein R.sup.14 is a hydrogen atom or a methyl group, and R.sup.15
is a hydrogen atom or a saturated or unsaturated hydrocarbon group
having a carbon number of 24 or less.
[0051] [12] The epoxy (meth)acrylate copolymer as described in [11]
above, wherein the acryl equivalent of the copolymer is from 300 to
3,500 g/eq.
[0052] [13] The epoxy (meth)acrylate copolymer as described in [11]
or [12] above, wherein the total content of the repeating units
represented by formulae (a1'), (a2'), (b1) and (b2) in the
copolymer is from 10 to 90 mol %, the content of the repeating unit
represented by formula (d) is from 5 to 90 mol %, and the total of
the total content of the repeating units represented by formulae
(a1'), (a2'), (b1) and (b2), and the content of the repeating unit
represented by formula (d) is 100 mol % or less.
[0053] [14] The epoxy (meth)acrylate copolymer as described in any
one of [11] to [13] above, wherein the copolymer is obtained by
reacting an epoxy group-containing copolymer containing at least
one of repeating units represented by the following formulae (a)
and (b):
##STR00011##
wherein each of R.sup.1 to R.sup.9 is a hydrogen atom or a methyl
group, and R.sup.12 is a hydrogen atom, a methyl group or a phenyl
group and a repeating unit represented by formula (d), with
(meth)acrylic acid.
[0054] [15] A process for producing the epoxy (meth)acrylate
copolymer described in [14] above, comprising
[0055] a step of radically-copolymerizing at least one of monomers
containing an epoxy group and an allyl group, represented by the
following formula (1) and (2):
##STR00012##
wherein each of R.sup.1 to R.sup.9 is a hydrogen atom or a methyl
group, and R.sup.12 is a hydrogen atom, a methyl group or a phenyl
group, with an olefin represented by the following formula (4):
##STR00013##
wherein R.sup.14 is a hydrogen atom or a methyl group, and R.sup.15
is a hydrogen atom or a saturated or unsaturated hydrocarbon group
having a carbon number of 24 or less, to provide an epoxy
group-containing copolymer containing at least one of repeating
units represented by formulae (a) and (b), and a repeating unit
represented by formula (d), and
[0056] a step of reacting (meth)acrylic acid with the epoxy
group-containing copolymer.
[0057] [16] The process for producing an epoxy (meth)acrylate
copolymer as described in [15] above, wherein the monomer
containing an epoxy group and an allyl group is at least one of
allyl 3,4-epoxycyclohexane-1-carboxylate, allyl
3,4-epoxy-1-methylcyclohexanecarboxylate and allyl
3,4-epoxy-6-phenylcyclohexanecarboxylate and the olefin is at least
one of ethylene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene.
[0058] [17] The epoxy (meth)acrylate copolymer as described in [15]
above, wherein the epoxy equivalent of the epoxy group-containing
copolymer is from 190 to 3,000 g/eq.
Effects of the Invention
[0059] The present invention can provide a novel epoxy
group-containing copolymer excellent in the electrical insulation,
promising utilization in the fields of, for example, an electrical
insulating material, such as a solder resist and an interlayer
insulating film, an encapsulant of IC and VLSI, and a laminated
sheet, and a production process thereof.
[0060] In addition, the epoxy (meth)acrylate copolymer of the
present invention is curable by light or heat, and provides a cured
product not only balanced between flexibility and toughness but
also excellent in the low dielectric characteristics, adherence,
water resistance, heat resistance, chemical resistance, electrical
insulation and the like, and therefore can be applied to a wide
range of fields including an electrical insulating material, such
as a solder resist and an interlayer insulating film, an
encapsulant of IC and VLSI, and a laminated sheet.
BRIEF DESCRIPTION OF THE DRAWINGS
[0061] FIG. 1 A .sup.13C-NMR spectrum of the oligomer obtained in
Example 1.
[0062] FIG. 2 A .sup.1H-NMR spectrum of the oligomer obtained in
Example 1.
[0063] FIG. 3 An IR spectrum of the oligomer obtained in Example
1.
[0064] FIG. 4 A DSC chart of a mixture of the oligomer obtained in
Example 1 and a cationic polymerization initiator.
[0065] FIG. 5 A .sup.1H-NMR spectrum of the compound (epoxy
(meth)acrylate copolymer) obtained in Example 27.
[0066] FIG. 6 A .sup.13C-NMR spectrum of the compound (epoxy
(meth)acrylate copolymer) obtained in Example 27.
[0067] FIG. 7 An IR spectrum of the compound (epoxy (meth)acrylate
copolymer) obtained in Example 27.
[0068] FIG. 8 A .sup.1H-NMR spectrum of the compound (epoxy
(meth)acrylate copolymer) obtained in Example 28.
[0069] FIG. 9 A .sup.13C-NMR spectrum of the compound (epoxy
(meth)acrylate copolymer) obtained in Example 28.
[0070] FIG. 10 An IR spectrum of the compound (epoxy (meth)acrylate
copolymer) obtained in Example 28.
[0071] FIG. 11 A graph showing the measurement results of
insulation resistance of Test Specimens a1 and b1 obtained in
Examples 38 and 39.
[0072] FIG. 12 A graph showing the measurement results of
insulation resistance of Test Specimens a2 and b2 obtained in
Examples 38 and 39 and Test Specimens c2 obtained in Comparative
Example 2.
MODE FOR CARRYING OUT THE INVENTION
[0073] The present invention is described in detail below.
[0074] The epoxy group-containing copolymer of the present
invention comprises:
[0075] at least one of repeating units containing an alicyclic
epoxy group, and an allyl group and/or a vinyl group, represented
by the following formulae (a), (b) and (c):
##STR00014##
wherein each of R.sup.1 to R.sup.11 is a hydrogen atom or a methyl
group, and R.sup.12 is a hydrogen atom, a methyl group or a phenyl
group, and
[0076] a repeating unit represented by the following formula
(d):
##STR00015##
wherein R.sup.14 is a hydrogen atom or a methyl group, and R.sup.15
is a hydrogen atom or a saturated or unsaturated hydrocarbon group
having a carbon number of 24 or less.
[0077] The repeating unit containing an alicyclic epoxy group, and
an allyl group and/or a vinyl group is preferably at least one of
the following repeating units:
##STR00016## ##STR00017##
[0078] The repeating unit represented by formula (d) is preferably
a repeating unit derived from an ethylene and/or an unsaturated
hydrocarbon having a carbon number of 8 or more.
[0079] The copolymer comprising at least one of repeating units
containing an alicyclic epoxy group, and an allyl group and/or a
vinyl group, represented by the above formulae (a), (b) and (c),
and at least one repeating unit represented by formula (d) is
obtained by radically-copolymerizing at least one of monomers
containing an epoxy group and an allyl or vinyl group, represented
by the following formulae (1), (2) and (3):
##STR00018##
wherein each of R.sup.1 to R.sup.11 is a hydrogen atom or a methyl
group, and R.sup.12 is a hydrogen atom, a methyl group or a phenyl
group, with
[0080] an olefin having a terminal double bond, represented by the
following formula (4):
##STR00019##
wherein R.sup.14 is a hydrogen atom or a methyl group, and R.sup.19
is a hydrogen atom or a saturated or unsaturated hydrocarbon group
having a carbon number of 24 or less.
[0081] The epoxy (meth)acrylate copolymer of the present invention
comprises at least one of repeating units represented by the
following formulae (a1'), (a2'), (b1) and (b2):
##STR00020##
wherein each of R.sup.1 to R.sup.9 and R.sup.12 is a hydrogen atom
or a methyl group, and R.sup.12 is a hydrogen atom, a methyl group
or a phenyl group, and a repeating unit represented by the
following formula (d):
##STR00021##
wherein R.sup.14 is a hydrogen atom or a methyl group, and R.sup.15
is a hydrogen atom or a saturated or unsaturated hydrocarbon group
having a carbon number of 24 or less.
[0082] This epoxy (meth)acrylate copolymer can be produced by a
process comprising
[0083] a step of radically-copolymerizing at least one of monomers
containing an epoxy group and an allyl group, represented by the
following formulae (1) and (2):
##STR00022##
wherein each of R.sup.1 to R.sup.9 is a hydrogen atom or a methyl
group, and R.sup.12 is a hydrogen atom, a methyl group or a phenyl
group, with an olefin represented by the following formula (4):
##STR00023##
wherein R.sup.14 is a hydrogen atom or a methyl group, and R.sup.15
is a hydrogen atom or a saturated or unsaturated hydrocarbon group
having a carbon number of 24 or less, to provide an epoxy
group-containing copolymer containing at least one of repeating
units represented by the following formulae (a) and (b):
##STR00024##
wherein each of R.sup.1 to R.sup.9 is a hydrogen atom or a methyl
group, and R.sup.12 is a hydrogen atom, a methyl group or a phenyl
group and a repeating unit represented by formula (d), and
[0084] a step of reacting (meth)acrylic acid with the epoxy
group-containing copolymer.
[0085] In the specification of the present invention, the term
"epoxy (meth)acrylate" indicates both an epoxy acrylate and an
epoxy methacrylate. Similarly, the term "(meth)acrylic acid"
indicates both methacrylic acid and acrylic acid.
[0086] In view of industrial use, the compound containing an
alicyclic epoxy group and an allyl group, represented by formula
(1) or (2), is preferably a monoepoxy compound obtained by using,
as a precursor, a reaction product of butadiene or cyclopentadiene
and (meth)acrylic acid, and after allyl esterification, performing
a regioselective epoxidization reaction. Examples thereof include
[0087] (meth)allyl 3,4-epoxycyclohexane-1-carboxylate, [0088]
(meth)allyl 3,4-epoxy-1-methylcyclohexanecarboxylate, [0089]
(meth)allyl 3,4-epoxy-6-methylcyclohexanecarboxylate, [0090]
(meth)allyl 3,4-epoxy-6-phenylcyclohexanecarboxylate, [0091]
(meth)allyl 5,6-epoxynorbornane-2-carboxylate, [0092] (meth)allyl
5,6-epoxy-2-methylnorbornane-2-carboxylate, [0093] (meth)allyl
5,6-epoxy-3-methylnorbornane-2-carboxylate, and (meth)allyl
5,6-epoxy-3-phenylnorbornane-2-carboxylate. More preferred examples
include allyl 3,4-epoxycyclohexane-1-carboxylate, allyl
3,4-epoxy-1-methylcyclohexanecarboxylate, and allyl
3,4-epoxy-6-phenylcyclohexanecarboxylate. Although the synthesis
method differs, other examples include a vinylcyclohexene oxide and
a limonene monooxide containing an alicyclic epoxy group and a
vinyl group represented by formula (3). Among these, at least one
of monomers containing an epoxy group and an allyl or vinyl group,
represented by the following formula (5):
##STR00025##
[0093] is preferred, and at least one of allyl
3,4-epoxycyclohexane-1-carboxylate and allyl
3,4-epoxy-1-methylcyclohexanecarboxylate is more preferred.
[0094] These compounds have an alicyclic epoxy group, and therefore
have high storage stability as compared with a glycidyl-type epoxy
compound, and their industrial use is facilitated. Furthermore, the
alicyclic epoxy group is higher in the cationic polymerizability
with a carboxyl group than a conventional glycidyl group. This is a
very advantageous feature in the field of electronic material
requiring curing at a lower temperature in a shorter amount of
time.
[0095] Specific preferred examples of the olefin compound having a
terminal double bond, represented by formula (4) include ethylene,
propylene, isobutene, 1-butene, 3-methyl-1-butene, 1-pentene,
2-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene,
1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, 4-vinylcyclohexene, 5-vinylnorbornene,
limonene and allylbenzene. The more preferred compound is at least
one of ethylene, 4-methyl-1-pentene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene,
4-vinylcyclohexene and limonene, more preferably at least one of
4-methyl-1-pentene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene and 1-octadecene.
[0096] The double bond of the epoxy compound is subjected to a
radical reaction with the olefin compound having a terminal double
bond composed only of a hydrocarbon, whereby a polyepoxy compound
excellent in the moisture absorption resistance can be
obtained.
[0097] Other copolymerizable monomers may also be used within the
range not adversely affecting the physical properties of the
copolymer (resin). Examples of such copolymerizable monomers
include an allyl group-containing compound, such as allyl
n-hexanoate, allyl cyclohexanecarboxylate, allyl
cyclohexylpropionate, allyl benzoate, allyl phenylacetate, allyl
phenoxyacetate, allyl trifluoroacetate, allyl methylcarbonate,
allyl ethylcarbonate, allyl methyl ether, allyl glycidyl ether,
allyl benzyl ether, allyloxytrimethylsilane, diallyl adipate,
diallyl maleate, diallyl malonate, diallyl itaconate,
1,2-diallyloxyethane and diallyl phthalate; a vinyl ester, such as
vinyl acetate, vinyl n-hexanoate, vinyl cyclohexanecarboxylate,
vinyl pivalate, vinyl n-dodecanoate, vinyl benzoate, vinyl
4-tert-butylbenzoate, vinyl phenylacetate, N-vinyl phthalimide,
vinyl cyclohexyl ether, vinyl trifluoroacetate,
vinyltrimethylsilane, vinyltriphenoxysilane, divinyldimethylsilane,
divinyloxyethane, divinyl diethylene glycol diether and
1,4-divinyloxybutane; an acrylic acid ester, such as methyl
acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate,
2-ethylhexyl acrylate, cyclohexyl acrylate, lauryl acrylate, benzyl
acrylate, phenoxyethyl acrylate, glycidyl acrylate, acrylonitrile,
N-methylaminomethyl acrylate and N,N-dimethylaminoethyl acrylate; a
methacrylic acid ester, such as methyl methacrylate, ethyl
methacrylate, isopropyl methacrylate, n-butyl methacrylate,
isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl
methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate,
benzyl methacrylate, phenoxyethyl methacrylate, glycidyl
methacrylate, methacrylonitrile, acrylamide, methacrylamide,
aminomethyl methacrylate, N-methylaminomethyl methacrylate,
N,N-dimethylaminomethyl methacrylate and 3,4-epoxycyclohexylmethyl
methacrylate; a styrene-based monomer, such as styrene,
vinyltoluene, .alpha.-methylstyrene, divinylbenzene and
4-vinylbiphenyl; and an N-substituted maleimide, such as
N-cyclohexylmaleimide and N-phenylmaleimide. Such monomers can be
suitably selected, and therefore various properties can be imparted
to a resin containing them as a component.
[0098] The blending ratio of these components in the radical
polymerization may be suitably determined according to the
hydrophobic group, aromatic ring, functional group and the like
intended to be included in the finally obtained epoxy resin
composition, and the amount of the epoxy compound used may also be
suitably determined depending on the content of the epoxy group
intended to be included in the objective epoxy resin. It is
preferable that the components are blended in such a ratio that the
total content of the repeating units represented by formulae (a),
(b) and (c) in the copolymer is from 10 to 90 mol %, the content of
the repeating unit represented by formula (d) is from 5 to 90 mol
%, and the total of the total content of the repeating units
represented by formulae (a), (b) and (c) and the content of the
repeating unit represented by formula (d) is 100 mass % or less. If
the total is less than 100 mol %, the rest derives from other
optional copolymerizable monomers used in combination, or a
modified monomeric product having a skeleton in which the epoxy
group in the repeating units represented by formulae (a), (b) and
(c) has been ring-opened by water, an alcohol or a carboxylic acid
mixed as an impurity or originated in an initiator during the
polymerization.
[0099] The epoxy equivalent of the copolymer of the present
invention is preferably from 190 to 3,000 g/eq., more preferably
from 250 to 1,000 g/eq. If the epoxy equivalent is less than 190,
the heat resistance, such as a glass transition temperature, may be
higher but flexibility is impaired, whereas if it exceeds 3,000,
the heat resistance lowers and due to reduction in the crosslinking
density, properties, such as solvent resistance, are deteriorated.
When the epoxy group-containing copolymer above is used, the acryl
equivalent of an epoxy (meth)acrylate copolymer as a final product
after the addition of (meth)acrylic acid would be from 300 to 3,500
g/eq. Incidentally, this acryl equivalent is a theoretical value
when all epoxy groups are converted to an acryloyl group.
[0100] The radical polymerization can be carried out without a
solvent. In the case of using a solvent, the solvent is not
particularly limited as long as it dissolves the monomers and
polymers, and the solvent is preferably inert to the epoxy group.
Examples of the solvent that can be used include aromatic
hydrocarbons, such as benzene, toluene and xylene; ketones, such as
acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers,
such as diethyl ether, dibutyl ether, tert-butyl methyl ether and
dioxane; esters, such as ethyl acetate, isobutyl acetate, ethylene
glycol monoacetate, propylene glycol monoacetate, propylene glycol
monomethyl ether acetate and dipropylene glycol monoacetate;
lactones, such as .gamma.-butyrolactone, .delta.-valerolactone and
.di-elect cons.-caprolactone; ethylene glycol monoalkyl ethers;
diethylene glycol monoalkyl ethers; ethylene glycol dialkyl ethers;
diethylene glycol dialkyl ethers, such as diethylene glycol
dimethyl ether and diethylene glycol diethyl ether; ethylene glycol
monoalkyl ether acetates; diethylene glycol monoalkyl ether
acetates; halogenated hydrocarbons, such as carbon tetrachloride
and chloroform; and alcohols, such as methanol, ethanol, 2-propanol
and cyclohexanol. Depending on the conditions, for example, amides,
such as dimethylformamide and dimethylacetamide, may also be used.
These solvents may be used individually or as a mixture.
[0101] As for the polymerization initiator, a conventional radical
polymerization initiator can be used, and for example, an azo type,
such as 2,2'-azobisisobutyronitrile and
2,2'-azobis-(2,4-dimethylvaleronitrile), and a peroxide type, such
as lauroyl peroxide, diisopropyl peroxydicarbonate,
bis(4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl
peroxy(2-ethylhexanoate),
1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane,
1,1-di(tert-butylperoxy)cyclohexane, tert-butyl
peroxyisopropylmonocarbonate, di-tert-butyl peroxide, di-tert-hexyl
peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, benzoyl
peroxide, tert-butyl peroxybenzoate and cumene hydroperoxide, may
be used individually or as a mixture. Among these, dialkyl
peroxides and dialkyl peroxydicarbonates are preferred, in view of
initiator efficiency and from the standpoint that the initiator
residue is less likely to accelerate hydrolysis or acidolysis of
the epoxy group. The polymerization initiator is preferably blended
in an amount of 0.1 to 30 mol % based on the total mole number of
monomers.
[0102] The reaction temperature varies depending on the kind of the
polymerization initiator but may be suitably selected between
-10.degree. C. and 220.degree. C., and in view of stability of the
epoxy group and easy handleability, the reaction temperature is
preferably from 10 to 160.degree. C.
[0103] As for the reaction pressure, particularly in the case of
reacting a compound which is gaseous at ordinary temperature, such
as ethylene, a pressure needs to be applied, whereas in the case of
using an olefin which is liquid at ordinary temperature, the
reaction can be carried out under atmospheric pressure.
[0104] The molecular weight of the copolymer produced is determined
depending on the reaction temperature, the adding rate of a monomer
or polymerization initiator, the monomer concentration, the kind of
monomer, and the like. The molecular weight of the epoxy
group-containing copolymer after radical polymerization is
preferably adjusted to from 400 to 8,000 in terms of the number
average molecular weight. If the molecular weight is too high,
workability decreases, whereas if it is excessively low, sufficient
property cannot be obtained after curing. When epoxy
(meth)acrylation is carried out using the epoxy group-containing
copolymer above, the number average molecular weight would be
approximately from 500 to 10,000.
[0105] Depending on the polymerization conditions, a diol
derivative resulting from hydrolysis of the epoxy group, or
particularly when using a perester, a glycol monoester derivative
resulting from reaction of the epoxy group with an organic acid
derived from the initiator may be by-produced. However, immixing of
these derivatives sometimes enhances the mechanical strength,
though the heat resistance may decrease, and this is not a problem
as long as good overall properties are maintained.
[0106] The epoxy group-containing copolymer obtained as above can
be designed to have various properties required of a solder resist,
an interlayer insulating film and the like by changing the
molecular weight and the kind of monomer introduced.
[0107] The reaction solution after radical polymerization may be
directly used in certain applications. For example, in the case of
using it for screen printing, polymerization is carried out in a
high boiling point solvent, such as diethylene glycol monoethyl
ether acetate and .gamma.-butyrolactone, and after additives, such
as silica, talc, a pigment, a defoaming agent and a leveling agent,
are added directly to the reaction solution, the mixture may be
kneaded by a dispersing machine, such as a three-roll mill, and
then used.
[0108] The thus-obtained reaction solution containing an epoxy
group-containing copolymer may be directly used in certain
applications. However, since the olefin compound represented by
formula (4) sometimes adversely affects the polymerization when
curing the copolymer by polymerizing an acryloyl group after the
addition of (meth)acrylic acid, the unreacted residual olefin
compound is preferably removed by distillation or the like. In
addition, since an epoxyallyl monomer or other coexisting low
molecular compounds sometimes deteriorate the properties or
increase the curing shrinkage percentage, it is a very effective
technique to distill off residual monomers or low molecular weight
oligomers by using a thin-film evaporation apparatus or a molecular
distillation apparatus.
[0109] For use in solventless applications, the olefin-based
residual monomer does not participate in the subsequent curing of
epoxy. Therefore, such a monomer may be distilled off, if
necessary, and after adding an initiator for epoxy directly to the
polymerization solution and further adding any required additives,
the resulting mixture may be shaped by casting polymerization or
the like.
[0110] After the polymerization, since an epoxy-based monomer
remains, it is an effective technique, particularly in the case of
improving the shrinkage percentage or enhancing the mechanical
properties, to distill off residual monomers or low molecular
weight oligomers by using a thin-film evaporation apparatus or a
molecular distillation apparatus.
[0111] The thin-film evaporation apparatus is an apparatus where a
processing solution in a thin film form is evaporated under vacuum
at a lower temperature without causing a thermal effect, and known
examples thereof include a falling film-type thin-film evaporation
apparatus, an agitated-type thin-film evaporation apparatus, and a
centrifugal thin-film evaporation apparatus. The apparatus is
generally operated under a pressure of 0.01 to 10 kPa at a
temperature of 50 to 250.degree. C.
[0112] The molecular evaporation apparatus is an apparatus where an
extremely high vacuum is maintained, the liquid film on the
evaporation surface is possibly thin so as to allow for very gentle
evaporation from the evaporation surface, the distance between the
evaporation surface and the condensation surface is not more than
the mean free path of a molecule, and the molecule is prevented as
much as possible from returning to the condensation surface by
keeping a sufficiently large temperature difference between the
evaporation surface and the condensation surface, and known
examples thereof include a pot molecular distillation apparatus, a
falling film-type molecular distillation apparatus, a centrifugal
molecular distillation apparatus and an experimental centrifugal
molecular distillation apparatus. The apparatus is generally
operated under a pressure of 2 kPa or less, usually from 0.0001 to
1 kPa, at a temperature of 50 to 250.degree. C., and even a
molecule having a molecular weight of approximately 1,000 can be
evaporated.
[0113] The epoxy group-containing copolymer obtained as above is
quantitatively determined for the epoxy group concentration by
measuring the epoxy equivalent and then reacted with (meth)acrylic
acid, whereby the objective epoxy (meth)acrylate resin can be
obtained. In this case, acrylic acid and methacrylic acid may be
used individually or in combination.
[0114] This reaction is carried out by blending an unsaturated
group-containing monocarboxylic acid in a ratio of 0.2 to 1.3 mol
per mol of the epoxy group usually at 50 to 150.degree. C. for 1 to
15 hours. Examples of a catalyst include amines, such as
triethylamine, dimethylbutylamine and tri-n-butylamine; quaternary
salts, such as tetramethylammonium salts, tetraethylammonium salts,
tetrabutylammonium salts and benzyltriethyl ammonium salts;
quaternary phosphonium salts; phosphines, such as
triphenylphosphines; and imidazoles, such as 2-methylimidazole and
2-ethyl-4-methylimidazole.
[0115] In the reaction, a reaction solvent, for example, alcohols,
such as methanol, ethanol, propanol, butanol, ethylene glycol,
methyl cellosolve and ethyl cellosolve; esters, such as methyl
cellosolve acetate and ethyl cellosolve acetate; a ketone-based
solvent, such as methyl ethyl ketone and methyl isobutyl ketone; a
lactone-based solvent, such as .gamma.-butyrolactone; and aromatic
compounds, such as benzene, toluene, chlorobenzene and
dichlorobenzene, can be used. A polymerizable dilute monomer, such
as styrene and methyl methacrylate, may also be used as a
solvent.
[0116] In the reaction, a polymerization inhibitor, such as
hydroquinone, methylhydroquinone, hydroquinone monomethyl ether,
4-methylquinoline, and phenothiazine, may be allowed to coexist in
the reaction system. Furthermore, for inhibiting a polymerization
reaction of an unsaturated bond, depending on the case, the
reaction may be carried out under a flow of air or the like. In
this case, an antioxidant, such as
2,6-di-tert-butyl-4-methylphenol, may be used in combination so as
to prevent an oxidation reaction by air.
[0117] The reaction solution after epoxy (meth)acrylation may be
directly used in certain applications. For example, in the case of
using it for screen printing, polymerization is carried out in a
high boiling point solvent, such as diethylene glycol monoethyl
ether acetate and .gamma.-butyrolactone, and after additives, such
as silica, talc, a pigment, a defoaming agent and a leveling agent,
are added directly to the reaction solution, the mixture may be
kneaded by a dispersing machine, such as a three-roll mill, and
then used.
[0118] Depending on the usage, the solvent may be distilled off,
and the residue may be used as a solventless photocurable or
thermosetting resin. In this case, the epoxy (meth)acrylate
copolymer of the present invention may be used alone or in
combination with another photosensitive (meth)acrylate compound,
and after blending a photopolymerization initiator in the same
manner as in the case of a conventional photosensitive
(meth)acrylate compound, may be cured by irradiating an active
energy ray.
[0119] Examples of the photosensitive (meth)acrylate compound
include hydroxyl group-containing acrylates, such as 2-hydroxyethyl
acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate and
dipentaerythritol pentaacrylate; water-soluble acrylates, such as
polyethylene glycol diacrylate and polypropylene glycol diacrylate;
polyfunctional polyester acrylates of a polyfunctional alcohol,
such as trimethylolpropane triacrylate, pentaerythritol
tetraacrylate and dipentaerythritol hexaacrylate; acrylates of an
ethylene oxide adduct or propylene oxide adduct of a polyfunctional
alcohol, such as trimethylolpropane and hydrogenated bisphenol A,
or a polyfunctional phenol, such as bisphenol A and biphenol;
polyfunctional or monofunctional polyurethane acrylates by
modifying the above-described hydroxyl group-containing acrylate
with an isocyanate; epoxyacrylates by adding (meth)acrylic acid to
bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl
ether or phenol novolak epoxy resins; and methacrylates
corresponding to the acrylates above. These may be used alone or in
combination of two or more thereof.
[0120] Examples of the photopolymerization initiator include
benzoin and benzoin alkyl ethers, such as benzoin, benzoin methyl
ether, benzoin ethyl ether and benzoin isopropyl ether;
acetophenones, such as acetophenone,
2,2-dimethoxy-2-phenylacetophenone,
2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone;
aminoacetophenones, such as
2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoaminopropanone-1,2-benzyl-2-
-dimethylamino-1-(4-morpholinophenyl)-butane-1-one and
N,N-dimethylaminoacetophenone; anthraquinones, such as
2-methylanthraquinone, 2-ethylanthraquinone,
2-tert-butylanthraquinone and 1-chloroanthraquinone; thioxanthones,
such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone,
2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals, such
as acetophenone dimethyl ketal and benzyl dimethyl ketal; organic
peroxides, such as benzoyl peroxide and cumene peroxide; thiol
compounds, such as 2,4,5-triarylimidazole dimer, riboflavin
tetrabutyrate, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and
2-mercaptobenzothiazole; organic halogen compounds, such as
2,4,6-tris-s-triazine, 2,2,2-tribromoethanol and
tribromomethylphenylsulfone; benzophenones or xanthones, such as
benzophenone and 4,4'-bisdiethylaminobenzophenone; alkylphenones,
such as 2,2-dimethoxy-1,2-diphenylethan-1-one,
1-hydroxy-cyclohexyl-phenyl-ketone,
2-hydroxy-2-methyl-1-phenyl-propan-1-one,
1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one
and
2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl--
propan-1-one; and 2,4,6-trimethylbenzoyldiphenylphosphine
oxide.
[0121] These conventionally-known and commonly-used
photopolymerization initiators may be used individually or as a
mixture of two or more kinds thereof, and a photoinitiation aid,
such as tertiary amines, e.g., ethyl N,N-dimethylaminobenzoate,
isoamyl N,N-dimethylaminobenzoate, pentyl-4-dimethylaminobenzoate,
triethylamine and triethanolamine, may be further added. A
titanocene compound, such as CGI-784 (produced by Ciba Specialty
Chemicals Inc.), having absorption in the visible light region may
be added so as to accelerate a photoreaction. Particularly
preferred examples of the photopolymerization initiator include
2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoaminopropanone-1,2-benzyl-2-
-dimethylamino-1-(4-morpholinophenyl)-butan-1-one and
1-hydroxy-cyclohexyl-phenyl-ketone, but the present invention is
not particularly limited thereto, and those capable of absorbing
light in the ultraviolet or visible light region and
radically-polymerizing an unsaturated group, such as a
(meth)acryloyl group, may be used individually or in combination of
a plurality of compounds, irrespective of a photopolymerization
initiator or a photoinitiation aid.
[0122] In addition, the epoxy (meth)acrylate copolymer of the
present invention may be used alone or in combination with another
(meth)acrylate or styrene compound and cured by a heat
polymerization method using an organic peroxide, an azo compound or
the like, or by an ambient-temperature polymerization method using
an organic peroxide and an accelerator.
[0123] Examples of the organic peroxide include tert-butyl
peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, benzoyl
peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide and
bis-4-tert-butylcyclohexyl peroxydicarbonate, and examples of the
azo compound include azobisisobutyronitrile, and such known
compounds may be used individually or as a mixture of two or more
kinds thereof. As for the accelerator, known accelerators, for
example, salts of a polyvalent metal, such as octylic acid salts or
naphthenic acid salts of cobalt, iron or manganese, and organic
amines, such as dimethylaniline, diethylaniline, p-toluidine and
ethanolamine, may be used individually or as a mixture of two or
more kinds thereof.
[0124] As described above, the epoxy (meth)acrylate copolymer of
the present invention alone or after blending with a photocurable
component and/or a thermosetting component is cured by irradiating
an active energy ray and/or heating, whereby a cured product
thereof can be obtained. For example, an epoxy (meth)acrylate resin
composition obtained by blending the epoxy (meth)acrylate copolymer
of the present invention and a photopolymerization initiator, or
further blending an epoxy resin and a curing agent, and optionally
further blending a sensitizer, a curing accelerator and the like,
can be easily formed into a cured product by the same method as a
conventionally known method. Furthermore, for example, the epoxy
(meth)acrylate copolymer of the present invention, a curing agent,
a filler and other additives are thoroughly mixed, if necessary,
using an extruder, a kneader, a roll or the like until the mixture
becomes uniform, thereby providing an epoxy (meth)acrylate resin
composition, and the epoxy (meth)acrylate resin composition is
melted, then cast or molded using a transfer molding machine or the
like, and further heated at 20 to 200.degree. C., whereby a cured
product can be obtained. A cured product can also be obtained by
dissolving the epoxy resin composition in a solvent, impregnating a
base material, such as glass fibers, carbon fibers, polyester
fibers, polyamide fibers, alumina fibers and paper, with the
solution, drying the impregnated substrate by heating, and
subjecting the resulting prepreg to heat press molding or
irradiation with an active energy ray. In the above-described epoxy
(meth)acrylate resin composition, various compounding ingredients,
such as an inorganic or organic filler, can be mixed, as
desired.
[0125] Furthermore, the epoxy (meth)acrylate resin composition, in
which the epoxy (meth)acrylate copolymer of the present invention,
a photopolymerization initiator, a curing agent and an optional
curing accelerator or the like are blended, may be dissolved in a
solvent and thereby adjusted to a viscosity suitable for the
coating method. Examples of such a solvent include ketones, such as
methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons, such
as toluene, xylene and tetramethylbenzene; glycol ethers, such as
cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl
carbitol, butyl carbitol, propylene glycol monomethyl ether,
propylene glycol monoethyl ether, dipropylene glycol diethyl ether
and triethylene glycol monoethyl ether; acetic acid esters, such as
ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve
acetate, carbitol acetate, butyl carbitol acetate, propylene glycol
monomethyl ether acetate and dipropylene glycol monomethyl ether
acetate; alcohols, such as ethanol, propanol, ethylene glycol and
propylene glycol; aliphatic hydrocarbons, such as octane and
decane; petroleum solvents, such as petroleum ether, petroleum
naphtha, hydrogenated petroleum naphtha and solvent naphtha. These
organic solvent may be used individually or as a mixture of two or
more kinds thereof. Incidentally, the blending amount of the
organic solvent can be a desired amount according to the coating
method.
[0126] Throughout the specification of the present invention, the
epoxy equivalent of the epoxy group-containing copolymer is
measured by the following method. In principle, hydrochloric acid
and an epoxy group are reacted, the residual amount of hydrochloric
acid is quantitatively determined by titration with an alkali, the
amount of hydrochloric acid reacted is determined from the value
obtained, and the amount of epoxy present in the resin is
calculated based thereon. For this purpose, a sample prepared, such
that the amount of the epoxy group is smaller than the amount of
hydrochloric acid to be used and is from 2 to 4 mmol equivalent, is
precisely weighed and put in a 200-ml stoppered conical flask, 25
mL of a 0.2 M hydrochloric acid-dioxane solution is added to this
vessel by using a hole pipette and dissolved, and the solution is
left standing at room temperature for 30 minutes. Subsequently, 10
ml of methyl cellosolve is added to wash the stopper and inner wall
of the conical flask, from 4 to 6 drops of a 0.1% cresol
red-ethanol solution as an indicator are added, and the mixture is
thoroughly stirred until the sample becomes uniform. The sample is
titrated with a 0.1 M potassium hydroxide-ethanol solution, and the
point when the blue-violet color of the indicator continues for 30
seconds is taken as the end point of neutralization. A value
obtained using the results in accordance to the following
calculation formula is defined as the epoxy equivalent of the
resin.
Epoxy equivalent(g/eq.)=(10000.times.S)/[(B-A).times.f]
[0127] S: Sampled amount (g) of sample
[0128] A: Used amount (ml) of 0.1 M potassium hydroxide-ethanol
solution
[0129] B: Used amount (ml) of 0.1 M potassium hydroxide-ethanol
solution in a blank test
[0130] f: Factor of 0.1 M potassium hydroxide-ethanol solution
[0131] In the measurement of the number average molecular weight
Mn, gel permeation chromatography (hereinafter, simply referred to
as "GPC") is used, and the molecular weight is determined by a
value converted to polystyrene (standard sample used: STANDARD
SM-105 produced by Showa Denko K.K.).
[0132] The measurement conditions of GPC are as follows.
[0133] Name of apparatus: HPLC Unit HSS-2000, manufactured by JASCO
Corporation
[0134] Column: Shodex Column LF-804
[0135] Mobile phase: tetrahydrofuran
[0136] Flow rate: 1.0 mL/min
[0137] Detector: RI-2031 Plus, manufactured by JASCO
Corporation
[0138] Temperature: 40.0.degree. C.
[0139] Amount of sample: sample loop: 100.mu. liter
[0140] Concentration of sample: adjusted to around 0.1 mass %
EXAMPLES
[0141] The present invention is described in greater detail below
by referring to Examples, but the present invention is not limited
thereto.
Example 1
[0142] In a personal organic synthesis device, PPV-4060 (simple
autoclave), manufactured by Tokyo Rikakikai Co., Ltd., 9.11 g (50
mmol) of allyl 3,4-epoxycyclohexane-1-carboxylate (hereinafter
simply referred to as "CEA"), 36.6 g of 1-decene (LINEALENE-10,
produced by Idemitsu Kosan Co., Ltd., purity: 96.6%, 250 mmol) and
2.238 g of di-tert-butyl peroxide (PERBUTYL-D, produced by NOF
Corporation, purity: 98%, 15 mmol) were charged, followed by
nitrogen purging. Thereafter, the reaction vessel was tightly
closed, and the reaction was allowed to proceed at 144.degree. C.
for 3 hours. After the reaction, the residual monomer amount was
measured by Gas Chromatography (GC) 6850 Series II manufactured by
Agilent Technologies. As a result, 55.8% of allyl
3,4-epoxycyclohexane-1-carboxylate and 25.4% of 1-decene were
reacted (copolymerization ratio: 1:2.28). The analysis of GPC
revealed that the number average molecular weight was 1,230 and the
weight average molecular weight was 1,980. CEA used herein as a raw
material was produced by the production process described in Kokai
No. 2006-316034.
[0143] The same operation was repeated eight times, and the
obtained polymerization solution was subjected to removal by
distillation of monomers and a small amount of low molecular weight
oligomers at a vacuum degree of 0.3 Pa and a column temperature of
110.degree. C. by using a molecular distillation apparatus (MS-FL
Special Model, manufactured by Taika Kogyo Co., Ltd.), whereby a
viscous oligomer having an epoxy equivalent of 572.4 was obtained.
The NMR (JNM EX-270, manufactured by JEOL Ltd.) spectrum of this
oligomer is shown in FIG. 1 (.sup.13C-NMR) and FIG. 2
(.sup.1H-NMR), and the IR (Spectrum GX, manufactured by Perkin
Elmer) spectrum is shown in FIG. 3.
[0144] As a result of .sup.13C-NMR analysis, a distinct peak
derived from the epoxy of epoxycyclohexane was observed in the
vicinity of 50 (ppm) and the signal derived from the allyl-position
carbon, which is observed at 64.330 (ppm) in the CEA monomer, was
shifted to the low magnetic field side of 64.700 (ppm) in
.sup.13C-NMR of the product. From these results, this compound
could be identified as an epoxy compound composed of a copolymer of
CEA monomer and 1-decene monomer. In addition, as a result of IR
analysis, absorption derived from the alicyclic epoxy and
characteristic absorption derived from the ester carbonyl were
observed at 1,172 cm.sup.-1 and 1,732 cm.sup.-1, respectively,
whereas absorption at 1,438 cm.sup.-1 derived from olefins of CEA
monomer and 1-decene monomer was not observed. From these results,
this compound could be identified as an epoxy compound having an
alicyclic epoxy unit and an ester unit in the molecular structure
and being composed of a copolymer of CEA monomer and 1-decene
monomer.
[0145] Furthermore, SANAID SI-100 L (cationic epoxy curing agent,
produced by Sanshin Chemical Industry Co., Ltd.) was added in an
amount of 1 part by mass per 100 parts by mass of the oligomer, and
DSC (204 F1, manufactured by NETZSCH) measurement was carried out.
FIG. 4 shows the results (measurement range: from 50.degree. C. to
350.degree. C., ramp rate: 10.degree. C./min). Since an exothermic
peak is observed, it is understood that a thermosetting reaction
occurred. In other words, cationic curability required as an
alicyclic epoxy is maintained, and even though a long chain olefin
has been copolymerized, a phenomenon that a curing reaction does
not occur due to steric hindrance or the like is not brought
about.
[0146] In addition, 2.67 g of anhydrous methylhexahydrophthalic
acid (HN-5500E, produced by Hitachi Chemical Industries, Ltd.) and
0.127 g of tetra-substituted phosphonium bromide (Epoxy Curing
Agent U-CAT 5003, produced by SAN-APRO Ltd.) were added to 10 g of
the oligomer above and after thoroughly mixing, the mixture was
sandwiched by glass plates with a 3-mm spacer therebetween and
cured at 60.degree. C. over 30 minutes, at 100.degree. C. over 2
hours, and at 150.degree. C. over 2 hours, to obtain a colorless
transparent cured plate.
Examples 2 to 24
[0147] Using various epoxy group-containing monomers (first
monomer) and olefins (second monomer), polymerization was carried
out under the condition of a charge weight of about 50 g, which is
similar to Example 1, by changing the polymerization conditions,
and the obtained results including the results of Example 1 are
shown in Table 1 below. It can be understood that copolymerization
proceeded under any of those conditions.
TABLE-US-00001 TABLE 1 Charge to Reaction Vessel Polymerization GC
Analysis Initiator Conditions Conversion Ratio First Monomer Second
Monomer Mole Preset Reaction First Example Kind Kind Kind Number
Temperature Time Monomer 1 CEA 1-decene PERBUTYL-D 5.0 mol % 144 3
hr 55.8% (produced (LINEALENE-10, (produced by Showa produced by by
NOF) Denko) Idemitsu Kosan) 2 CEA 1-dodecene PERBUTYL-D 5.0 mol %
144 3 hr 53.8% (produced (LINEALENE-12, (produced by Showa produced
by by NOF) Denko) Idemitsu Kosan) 3 CEA 1-tetradecene PERBUTYL-D
5.0 mol % 144 3 hr 58.2% (produced (LINEALENE-14, (produced by
Showa produced by by NOF) Denko) Idemitsu Kosan) 4 CEA 1-hexadecene
PERBUTYL-D 5.0 mol % 144 3 hr 35.9% (produced (LINEALENE-16,
(produced by Showa produced by by NOF) Denko) Idemitsu Kosan) 5 CEA
1-octadecene PERBUTYL-D 6.25 mol % 144 3 hr 43.7% (produced
(LINEALENE-18, (produced by Showa produced by by NOF) Denko)
Idemitsu Kosan) 6 CEA 1-hexene PERBUTYL-D 5.0 mol % 144 3 hr 30.2%
(produced (LINEALENE-6, (produced by Showa produced by by NOF)
Denko) Idemitsu Kosan) 7 CEA 1-octene PERBUTYL-D 5.0 mol % 144 3 hr
60.8% (produced (LINEALENE-8, (produced by Showa produced by by
NOF) Denko) Idemitsu Kosan) 8 CEA 2-methyl- PERBUTYL-D 5.0 mol %
144 3 hr 36.0% (produced pentene-1 (produced by Showa (produced by
by NOF) Denko) Tokyo Chemical) 9 CEA 4-methyl- PERBUTYL-D 5.0 mol %
144 3 hr 60.5% (produced pentene-1 (produced by Showa (produced by
by NOF) Denko) Tokyo Chemical) 10 CEA limonene PERBUTYL-D 5.0 mol %
144 3 hr 9.9% (produced (produced by (produced by Showa Ogawa &
Co., by NOF) Denko) Ltd.) 11 CEA 4-vinyl- PERBUTYL-D 5.0 mol % 144
3 hr 9.3% (produced cyclohexene (produced by Showa (produced by by
NOF) Denko) Tokyo Chemical) 12 CEA 5-vinyl- PERBUTYL-D 5.0 mol %
144 3 hr 17.9% (produced norbornene (produced by Showa (produced by
by NOF) Denko) Tokyo Chemical) 13 limonene 1-dodecene PERBUTYL-D
5.0 mol % 160 1 hr 21.3% monooxide (LINEALENE-12, (produced
(produced produced by by NOF) by Showa Idemitsu Kosan) Denko) 14
vinylcyclo- 1-dodecene PERBUTYL-D 5.4 mol % 144 3 hr 9.0% hexene
(LINEALENE-12, (produced oxide produced by by NOF) (produced
Idemitsu Kosan) by Daicel Chemical) 15 CEA 1-dodecene PERBUTYL-D
5.0 mol % 144 3 hr 57.4% (produced (LINEALENE-12, (produced by
Showa produced by by NOF) Denko) Idemitsu Kosan) 16 CEA 1-dodecene
PERBUTYL-D 5.0 mol % 144 3 hr 66.4% (produced (LINEALENE-12,
(produced by Showa produced by by NOF) Denko) Idemitsu Kosan) 17
CEA 1-dodecene PERBUTYL-D 6.0 mol % 144 3 hr 45.3% (produced
(LINEALENE-12, (produced by Showa produced by by NOF) Denko)
Idemitsu Kosan) 18 CEA 1-dodecene PERBUTYL-D 3.0 mol % 144 3 hr
35.2% (produced (LINEALENE-12, (produced by Showa produced by by
NOF) Denko) Idemitsu Kosan) 19 CEA 1-dodecene PERBUTYL-D 7.0 mol %
144 3 hr 63.4% (produced (LINEALENE-12, (produced by Showa produced
by by NOF) Denko) Idemitsu Kosan) 20 CEA 1-dodecene PERBUTYL-D 5.0
mol % 144 2 hr 48.3% (produced (LINEALENE-12, (produced by Showa
produced by by NOF) Denko) Idemitsu Kosan) 21 CEA 1-dodecene
PERBUTYL-D 5.0 mol % 144 4 hr 54.4% (produced (LINEALENE-12,
(produced by Showa produced by by NOF) Denko) Idemitsu Kosan) 22
CEA 1-dodecene PERBUTYL-D 5.0 mol % 130 6 hr 33.6% (produced
(LINEALENE-12, (produced by Showa produced by by NOF) Denko)
Idemitsu Kosan) 23 CEA 1-dodecene PERBUTYL-D 5.0 mol % 160 1 hr
60.4% (produced (LINEALENE-12, (produced by Showa produced by by
NOF) Denko) Idemitsu Kosan) 24 CEA 1-dodecene PERHEXA- 5.0 mol %
106 3 hr 37.7% (produced (LINEALENE-12, TMH by Showa produced by
(produced Denko) Idemitsu Kosan) by NOF) GC Analysis Conversion
Ratio Second/First Second Molar Ratio GPC Example Monomer Charge
Reaction Mn Mw Mw/Mn 1 25.4% 5.00 2.28 1230 1978 1.61 2 21.1% 5.00
1.96 1455 2218 1.52 3 26.1% 5.00 2.24 1779 2716 1.53 4 4.9% 5.00
0.69 1986 2793 1.41 5 5.8% 5.00 0.66 2226 3087 1.39 6 16.2% 5.00
2.68 820 1311 1.60 7 25.2% 5.00 2.07 971 1601 1.65 8 39.1% 5.00
5.44 621 859 1.38 9 36.6% 5.00 3.03 894 1428 1.60 10 6.2% 5.00 3.13
358 483 1.25 11 10.1% 5.00 5.42 386 433 1.12 12 19.1% 5.00 5.35 791
1313 1.66 13 25.8% 5.00 6.06 1220 1714 1.40 14 12.5% 5.00 6.35 1131
1586 1.40 15 26.8% 2.00 0.93 1437 2254 1.57 16 31.9% 4.00 1.92 1444
2335 1.62 17 18.3% 6.00 2.42 1451 2274 1.57 18 13.9% 5.00 1.97 1340
2382 1.78 19 30.1% 5.00 2.37 1490 2422 1.63 20 19.4% 5.00 2.01 1371
2139 1.56 21 23.3% 5.00 2.14 1390 2234 1.61 22 11.2% 5.00 1.67 1459
2182 1.50 23 27.9% 5.00 2.31 1437 2164 1.51 24 9.6% 5.00 1.28 871
1331 1.53 PERHEXA-TMH:
1,1-(di-tert-hexylperoxy)-3,3,5-trimethylcyclohexane
Evaluation as Thermosetting Composition for Overcoat
Preparation of Thermosetting Resin Composition
Example 25
[0148] Out of the components shown below, components except for the
fluorine-containing surfactant and the leveling agent were blended
with the copolymer obtained in Example 1, and the mixture was
kneaded using a three-roll mill. After kneading by a three-roll
mill, the surfactant and the leveling agent were added thereto and
mixed by a resin mixer to prepare a thermosetting resin
composition.
TABLE-US-00002 Copolymer of Example 1 28.6 parts by mass Acid
anhydride: HN-5500E 8.4 parts by mass (produced by Hitachi Chemical
Industries, Ltd.) Curing agent: 2E4MZ (produced 0.37 parts by mass
by Shikoku Chemicals Corp.) Thixotropic agent: Aerosil R974 1.85
parts by mass (produced by Nippon Aerosil Co., Ltd.) Barium
sulfate: B94 (produced 7.4 parts by mass by Sakai Chemical Industry
Co., Ltd.) Silicone powder: X-52-854 1.85 parts by mass (produced
by Shin-Etsu Chemical Co., Ltd.) Fluorine-containing surfactant:
0.11 parts by mass PolyFOX PF6520 (produced by OMNOVA) Leveling
agent: DISPARLON 230 0.56 parts by mass HF (produced by Kusumoto
Chemicals, Ltd.)
<Evaluation of Cured Product>
[Long-Term Reliability of Electrical Insulation]
[0149] A commercially available substrate (IPC standard) IPC-C (100
.mu.m-pitch comb-type pattern, line/space=50.mu./50 .mu.m) was used
as a base material, and the thermosetting resin composition above
was printed on the base material under the conditions of a screen
plate of ST250-30, a printing speed of 100 mm/sec, a clearance
between printing plate and base material of 2.0 mm, a squeegee
hardness of 80.degree. and a squeegee angle of 70.degree., then
dried at 80.degree. C. for 30 minutes and further thermally cured
at 150.degree. C. for 1 hour. This substrate was left standing for
a predetermined time in a high-temperature high-humidity atmosphere
(85.degree. C., relative humidity: 85%) while applying a bias
voltage of 100 V and evaluated for the insulation resistance value
and the presence or absence of migration.
[0150] The insulation resistance value before the treatment in a
high-temperature high-humidity atmosphere was 10.sup.10.OMEGA. or
more and even after 200 hours of the treatment in a
high-temperature high-humidity atmosphere, the insulation
resistance value was kept at 10.sup.10.OMEGA.. In addition,
migration was not recognized even after 200 hours of the treatment
in a high-temperature high-humidity atmosphere. In the present
invention, a copolymer based on a compound having an alicyclic
epoxy group epoxidized through hydrogen peroxide oxidation or
peracetic acid oxidation but not by a halohydrin method is used,
and therefore the electrical insulation of the cured plate obtained
was good. It can be expected that by copolymerizing a monomer
containing an epoxy group and an allyl or vinyl group with a
long-chain .alpha.-olefin, a soft cured product with high
hydrophobicity, which derives from a liquid before curing, is
obtained after curing.
Example 26
[0151] In a 1 L-volume four-neck flask equipped with a thermometer,
an oil bath and a reflux condenser tube, 300.0 (g) of CEA (produced
by Showa Denko K.K., 1.65 mol) and 277.1 (g) of 1-dodecene
(produced by Idemitsu Kosan Co., Ltd., 1.65 mol) were charged and
mixed with stirring under nitrogen atmosphere. The oil bath was
heated while continuing the stirring and the internal temperature
was set to 160.degree. C. Thereto, 24.6 (g) of di-tert-butyl
peroxide (produced by NOF Corporation) was added dropwise over 1
hour by a dropping funnel, and the mixture was ripened for 2 hours.
After the reaction, the residual monomer amount was measured by Gas
Chromatography 6850GC Series II manufactured by Agilent
Technologies. As a result, 85.8% of CEA and 57.6% of 1-decene were
reacted (copolymerization ratio: 1:0.67).
[0152] The same operation was repeated twice, and the obtained
polymerization solution was subjected to removal by distillation of
monomers and a small amount of low molecular weight oligomers at a
vacuum degree of 0.3 Pa and a column temperature of 110.degree. C.
by using a molecular distillation apparatus (MS-FL Special Model,
manufactured by Taika Kogyo Co., Ltd.), whereby a viscous oligomer
having an epoxy equivalent of 323.3 was obtained.
[0153] In addition, 318.18 (g) of anhydrous methylhexahydrophthalic
acid (HN-5500E, produced by Hitachi Chemical Industries, Ltd.) and
9.92 (g) of 2-ethyl-4-methylimidazole (produced by Shikoku
Chemicals Corp.) were added to 673.5 (g) of the oligomer above and
after mixing, the mixture was vacuum defoamed to prepare Curing
Solution a. SUS molds sandwiching a spacer having a predetermined
thickness were heated at 60.degree. C., and Curing Solution a was
poured thereinto and cured at 80.degree. C. over 1 hour, at
120.degree. C. over 2 hours, and at 150.degree. C. over 2 hours, to
obtain a colorless transparent cured plate. The cured plates
obtained were 4 square plates of 220 mm.times.220 mm.times.3 mm and
12 block plates of 100 mm.times.10 mm.times.4 mm.
[0154] A JIS K7113 No. 1 test specimen was prepared from the cured
plate obtained above and subjected to a tensile test (strength,
elongation) by the method in accordance with JIS K7113 using
STROGRAPH TD manufactured by Toyo Seiki Seisaku-Sho, Ltd., under
the conditions of a test speed of 5 mm/min, a marker-to-marker
distance of 50 mm, a chuck-to-chuck distance of 115 mm, a test
temperature of 23.degree. C. and a test number of n=5. The results
are shown in Table 2 below.
[0155] In addition, a test specimen of 100 mm.times.100 mm.times.3
mm was prepared from the cured plate obtained above, left standing
in an environment of 23.+-.2.degree. C. and 50.+-.5% RH for 48
hours for conditioning, and then subjected to an insulation
resistance test by the method in accordance with JIS K6911:1995
using a digital ultrahigh resistance/micro current ammeter, R8340A,
manufactured by Advantest Corporation (main electrode: 50 mm in
diameter, inner diameter/outer diameter of guard electrode=70 mm/80
mm) under the conditions of an applied voltage of 500 (V), an
applying time of 1 minute, a test temperature of 23.degree. C. and
a test number of n=3. The results are shown in Table 2 below.
[0156] Furthermore, a test specimen of 100 mm.times.100 mm.times.3
mm was prepared from the cured plate obtained above and subjected
to an arc resistance test by the method in accordance with ASTM
D495 using an arc resistance tester, Model YST-1621, manufactured
by Yamayo Measuring Tools Co., Ltd., under the conditions of a test
temperature of 23.degree. C. and a test number of n=3. The results
are shown in Table 2 below.
[0157] In addition, a test specimen of 100 mm.times.100 mm.times.3
mm was prepared from the cured plate obtained above and measured
for the water absorption ratio by the method in accordance with JIS
K7209 Method A under the condition of a test number of n=3. In
particular, the test specimen was dried in a drier at 50.degree. C.
for 24 hours and then allowed to cool in a desiccator, and the
initial weight (M1) was measured by an electronic balance.
Thereafter, the test specimen was immersed in distilled water for
24 hours and taken out, and after wiping off the water on the
sample surface with a filter paper, the weight (M2) after water
absorption was measured. The water absorption ratio was calculated
by introducing the measured weights into the following formula:
Water absorption ratio(%)={(M2-M1)/M1}.times.100
[0158] The results are shown in Table 2 below.
Comparative Example 1
[0159] 139 Parts by weight of Celloxide 2021P (produced by Daicel
Chemical Industries, Ltd.), 164 parts by weight of anhydrous
methylhexahydrophthalic acid (HN-5500E, produced by Hitachi
Chemical Industries, Ltd.) and 6.06 parts by weight of
2-ethyl-4-methylimidazole (produced by Shikoku Chemicals Corp.)
were mixed, and the mixture was vacuum defoamed to prepare Curing
Solution b. Similarly to Example 26, Curing Solution b was poured
into molds heated at 100.degree. C., and then cured at 100.degree.
C. over 1 hour, at 120.degree. C. over 6 hours, at 150.degree. C.
over 1 hour, and at 180.degree. C. over 1 hour.
[0160] The specimens similar to those in Example 26 were prepared
from the cured plate obtained above and subjected to a tensile test
(strength, elongation), an insulation resistance test, an arc
resistance test and measurement of a water absorption ratio. The
results are shown together in Table 2 below.
TABLE-US-00003 TABLE 2 Insulation Tensile Test Resistance Test Arc
Water Elon- Surface Volume Resis- Absorp- ga- Resis- Resis- tance
tion Strength tion tance tance Test Ratio MPa % .OMEGA. .OMEGA./cm
sec % Example 26 40.2 4.0 1.2 .times. 10.sup.17 2.4 .times.
10.sup.16 125 0.18 Comparative 40.0 1.6 1.4 .times. 10.sup.16 5.4
.times. 10.sup.15 110 0.60 Example 1
[0161] It can be understood that the epoxy resin obtained in the
present invention as above is enhanced in the flexibility,
insulation resistance and arc resistance, as compared with the
conventional alicyclic epoxy compound, and further has a low water
absorption ratio.
Synthesis Example 1
[0162] In a personal organic synthesis device, PPV-4060 (simple
autoclave), manufactured by Tokyo Rikakikai Co., Ltd., 21.9 g (120
mmol) of allyl 3,4-epoxycyclohexane-1-carboxylate (hereinafter
simply referred to as "CEA", produced by Showa Denko K.K.), 34.25 g
of 1-octene (LINEALENE-8, produced by Idemitsu Kosan Co., Ltd.,
purity: 98.3%, 300 mmol) and 3.13 g of di-tert-butyl peroxide
(PERBUTYL-D, produced by NOF Corporation, purity: 98%, 21 mmol)
were charged, followed by nitrogen purging. Thereafter, the
reaction vessel was tightly closed, and the reaction was allowed to
proceed at 160.degree. C. for 3 hours. After the reaction, the
residual monomer amount was measured by Gas Chromatography (GC)
6850 Series II manufactured by Agilent Technologies. As a result,
75.3% of CEA and 37.3% of 1-octene were reacted (copolymerization
ratio: CEA/1-octene=1/1.24).
[0163] The same experiment was repeated four times, and the
obtained polymerization solution was subjected to removal by
distillation of monomers at a vacuum degree of 20 hPa and a water
temperature of 25 to 60.degree. C. by using a rotary evaporator,
N-1000, manufactured by Tokyo Rikakikai Co., Ltd. Furthermore,
residual monomers and a small amount of low molecular weight
oligomers were distilled off at a vacuum degree of 0.3 Pa and a
column temperature of 100.degree. C. by using a molecular
distillation apparatus, MS-FL Special Model, manufactured by Taika
Kogyo Co., Ltd., to obtain a viscous oligomer having an epoxy
equivalent of 388.6. The analysis of GPC revealed that the number
average molecular weight was 1,200 and the weight average molecular
weight was 1,980. CEA used herein as a raw material was produced by
the production process described in Kokai No. 2006-316034.
Synthesis Example 2
[0164] In a personal organic synthesis device, PPV-4060 (simple
autoclave), manufactured by Tokyo Rikakikai Co., Ltd., 25.5 g of
CEA (produced by Showa Denko K.K., 140 mmol), 42.55 g of
4-methyl-1-pentene (4 MP-1, produced by Mitsui Chemicals, Inc.,
purity: 98%, 300 mmol) and 3.66 g of di-tert-butyl peroxide
(PERBUTYL-D, produced by NOF Corporation, purity: 98%, 24.5 mmol)
were charged, followed by nitrogen purging. Thereafter, the
reaction vessel was tightly closed, and the reaction was allowed to
proceed at 160.degree. C. for 3 hours. After the reaction, the
residual monomer amount was measured by Gas Chromatography (GC)
6850 Series II manufactured by Agilent Technologies. As a result,
76.6% of CEA and 46.7% of 4-methyl-1-pentene were reacted
(copolymerization ratio: CEA/4-methyl-1-pentene=1/1.52).
[0165] The same experiment was repeated four times, and the
obtained polymerization solution was subjected to removal by
distillation of monomers at a vacuum degree of 20 hPa and a water
temperature of 25 to 60.degree. C. by using a rotary evaporator,
N-1000, manufactured by Tokyo Rikakikai Co., Ltd. Furthermore,
residual monomers and a small amount of low molecular weight
oligomers were distilled off at a vacuum degree of 0.3 Pa and a
column temperature of 120.degree. C. by using a molecular
distillation apparatus, MS-FL Special Model, manufactured by Taika
Kogyo Co., Ltd., to obtain a viscous oligomer having an epoxy
equivalent of 320.8. The analysis of GPC revealed that the number
average molecular weight was 1,100 and the weight average molecular
weight was 1,760.
Synthesis Example 3
[0166] In a 1 L-volume four-neck flask equipped with a reflux tube,
a thermometer and a ball cock, 167.6 g of CEA (produced by Showa
Denko K.K., 0.92 mol), 405.8 g of 1-dodecene (LINEALENE-12,
produced by Idemitsu Kosan Co., Ltd., purity: 95.4%, 2.3 mol) and
24.0 g of di-tert-butyl peroxide (PERBUTYL-D, produced by NOF
Corporation, purity: 98%, 0.16 mol) were charged. This mixed
solution was stirred under heating in an oil bath at 160.degree. C.
and thereby reacted for 3 hours. After the reaction, the residual
monomer amount was measured by Gas Chromatography (GC) 6850 Series
II manufactured by Agilent Technologies. As a result, 76.5% of CEA
and 43.7% of 1-dodecene were reacted (copolymerization ratio:
CEA/1-dodecene=1/1.43).
[0167] From the obtained polymerization solution, monomers were
distilled off at a vacuum degree of 2 Torr and a bath temperature
of 150.degree. C. by using a vacuum pump. Furthermore, residual
monomers and a small amount of low molecular weight oligomers were
distilled off at a vacuum degree of 0.3 Pa and a column temperature
of 120.degree. C. by using a molecular distillation apparatus,
MS-FL Special Model, manufactured by Taika Kogyo Co., Ltd., to
obtain a viscous oligomer having an epoxy equivalent of 480.8. The
analysis of GPC revealed that the number average molecular weight
was 1,600 and the weight average molecular weight was 2,550.
Synthesis Example 4
[0168] In a 1 L-volume four-neck flask equipped with a reflux tube,
a thermometer, a dropping funnel and a ball cock, 180.0 g of CEA
(produced by Showa Denko K.K., 0.99 mol), 103.3 g of 1-tetradecene
(LINEALENE-14, produced by Idemitsu Kosan Co., Ltd., purity: 93.9%,
0.49 mol) and 11.1 g of di-tert-butyl peroxide (PERBUTYL-D,
produced by NOF Corporation, purity: 98%, 74 mmol) were charged.
This mixed solution was stirred under heating in an oil bath at
160.degree. C. and thereby reacted for 3 hours. After the reaction,
the residual monomer amount was measured by Gas Chromatography (GC)
6850 Series II manufactured by Agilent Technologies. As a result,
77.3% of CEA and 48.3% of 1-tetradecene were reacted
(copolymerization ratio: CEA/1-tetradecene=1/0.31).
[0169] From the obtained polymerization solution, monomers were
distilled off at a vacuum degree of 2 Torr and a bath temperature
of 150.degree. C. by using a vacuum pump. Furthermore, monomers and
a small amount of low molecular weight oligomers were distilled off
at a vacuum degree of 0.3 Pa and a column temperature of
100.degree. C. by using a molecular distillation apparatus, MS-FL
Special Model, manufactured by Taika Kogyo Co., Ltd., to obtain a
viscous oligomer having an epoxy equivalent of 276.1. The analysis
of GPC revealed that the number average molecular weight was 1,500
and the weight average molecular weight was 2,900.
Synthesis Example 5
[0170] In a 1 L-volume four-neck flask equipped with a reflux tube,
a thermometer, a dropping funnel and a ball cock, 91.1 g of CEA
(produced by Showa Denko K.K., 0.50 mol), 441.1 g of 1-dodecene
(LINEALENE-12, produced by Idemitsu Kosan Co., Ltd., purity: 95.4%,
2.50 mol) and 22.4 g of di-tert-butyl peroxide (PERBUTYL-D,
produced by NOF Corporation, purity: 98%, 0.15 mol) were charged.
This mixed solution was stirred under heating in an oil bath at
160.degree. C. and thereby reacted for 3 hours. After the reaction,
the residual monomer amount was measured by Gas Chromatography (GC)
6850 Series II manufactured by Agilent Technologies. As a result,
76.6% of CEA and 39.6% of 1-dodecene were reacted (copolymerization
ratio: CEA/1-dodecene=1/2.59).
[0171] From the obtained polymerization solution, monomers were
distilled off at a vacuum degree of 2 Torr and a bath temperature
of 150.degree. C. by using a vacuum pump. Furthermore, monomers and
a small amount of low molecular weight oligomers were distilled off
at a vacuum degree of 0.3 Pa and a column temperature of 90.degree.
C. by using a molecular distillation apparatus, MS-FL Special
Model, manufactured by Taika Kogyo Co., Ltd., to obtain a viscous
oligomer having an epoxy equivalent of 778.2. The analysis of GPC
revealed that the number average molecular weight was 1,500 and the
weight average molecular weight was 2,400.
Synthesis Example 6
[0172] In a 1 L-volume four-neck flask equipped with a reflux tube,
a thermometer, a dropping funnel and a ball cock, 236.9 g of CEA
(produced by Showa Denko K.K., 1.30 mol), 229.4 g of 1-dodecene
(LINEALENE-12, produced by Idemitsu Kosan Co., Ltd., purity: 95.4%,
1.30 mol) and 19.4 g of di-tert-butyl peroxide (PERBUTYL-D,
produced by NOF Corporation, purity: 98%, 0.13 mol) were charged.
This mixed solution was stirred under heating in an oil bath at
160.degree. C. and thereby reacted for 3 hours. After the reaction,
the residual monomer amount was measured by Gas Chromatography (GC)
6850 Series II manufactured by Agilent Technologies. As a result,
71.0% of CEA and 43.1% of 1-dodecene were reacted (copolymerization
ratio: CEA/1-dodecene=1/0.61).
[0173] From the obtained polymerization solution, monomers were
distilled off at a vacuum degree of 2 Torr and a bath temperature
of 150.degree. C. by using a vacuum pump.
[0174] Furthermore, monomers and a small amount of low molecular
weight oligomers were distilled off at a vacuum degree of 0.3 Pa
and a column temperature of 100.degree. C. by using a molecular
distillation apparatus, MS-FL Special Model, manufactured by Taika
Kogyo Co., Ltd., to obtain a viscous oligomer having an epoxy
equivalent of 328.1. The analysis of GPC revealed that the number
average molecular weight was 1,400 and the weight average molecular
weight was 2,200.
Synthesis Example 7
[0175] In a 500 mL-volume polyethylene vessel, 120 g of CEA
(produced by Showa Denko K.K., 0.66 mol), 138.56 g of
4-methyl-1-pentene (produced by Mitsui Chemicals, Inc., 1.65 mol)
and 16.68 g of di-tert-butyl peroxide (produced by NOF Corporation,
0.11 mol) were charged and thoroughly mixed to prepare a synthesis
raw material solution. In a personal organic synthesis device,
PPV-4060 (simple autoclave), manufactured by Tokyo Rikakikai Co.,
Ltd., 68.88 g of the synthesis raw material solution was charged,
and the inside of the reaction vessel was purged with nitrogen.
Thereafter, the reaction vessel was tightly closed, and the
reaction was allowed to proceed at an outside temperature of
160.degree. C. for 3 hours. After the reaction, the reaction
solution was subjected to quantitative determination of the
residual monomer amount by 7890AGC manufactured by Agilent
Technologies. As a result, 79.03% of CEA and 49.28% of
4-methyl-1-pentene were reacted and the copolymerization ratio was
CEA/4-methyl-1-pentene=1/1.37.
[0176] Reaction solutions obtained by repeating the same reaction
three times were combined, and the resulting solution was purified
by removing monomers and low molecular weight oligomers in the same
manner as in Synthesis Example 2 to obtain a viscous
CEA-4-methyl-1-pentene copolymer having an epoxy equivalent of
307.76.
Synthesis Example 8
[0177] A viscous CEA-1-dodecene copolymer having an epoxy
equivalent of 350.98 was obtained by performing the same Operation
as in Synthesis Example 6 except for using 770.92 g of CEA, 712.01
g of 1-dodecene and 61.82 g of di-tert-butyl peroxide.
Example 27
[0178] 3.0 Gram of the CEA-1-dodecene copolymer of Synthesis
Example 3, 0.54 g of methacrylic acid, 0.03 g of
triphenylphosphine, 0.0071 g of hydroquinone monomethyl ether and
3.6 g of toluene were charged and in an oil bath at 120.degree. C.
the reaction was allowed to proceed for 2 hours. From the obtained
reaction solution, toluene was distilled off at a vacuum degree of
1 Torr and an oil bath temperature of 100.degree. C. by using a
vacuum pump.
[0179] The .sup.1H-NMR spectrum, .sup.13C-NMR spectrum and IR
spectrum of the obtained compound are shown in FIGS. 5 to 7,
respectively. From these results, the compound obtained was
identified as a mixture containing repeating units of formulae
(a1') and (a2') wherein each of R.sup.1 to R.sup.7 and R.sup.12 is
a hydrogen atom, and R.sup.13 is a methyl group.
Example 28
[0180] 3.0 Gram of the CEA-4-methyl-1-pentene copolymer of
Synthesis Example 2, 0.81 g of methacrylic acid, 0.03 g of
triphenylphosphine, 0.0077 g of hydroquinone monomethyl ether and
3.8 g of toluene were charged and in an oil bath at 120.degree. C.
the reaction was allowed to proceed for 2 hours. From the obtained
reaction solution, toluene was distilled off at a vacuum degree of
1 Torr and an oil bath temperature of 100.degree. C. by using a
vacuum pump.
[0181] The .sup.1H-NMR spectrum, .sup.13C-NMR spectrum and IR
spectrum of the obtained compound are shown in FIGS. 8 to 10,
respectively. From these results, the compound obtained was
identified as a mixture containing repeating units of formulae
(a1') and (a2') wherein each of R.sup.1 to R.sup.7 and R.sup.12 is
a hydrogen atom, and R.sup.13 is a methyl group.
Example 29
[0182] 3.0 Gram of the CEA-4-methyl-1-pentene copolymer of
Synthesis Example 2, 0.67 g of acrylic acid, 0.03 g of
triphenylphosphine, 0.0074 g of hydroquinone monomethyl ether and
3.7 g of toluene were charged and in an oil bath at 120.degree. C.
the reaction was allowed to proceed for 2 hours. From the obtained
reaction solution, toluene was distilled off at a vacuum degree of
1 Torr and an oil bath temperature of 100.degree. C. by using a
vacuum pump to obtain a mixture containing repeating units of
formulae (a1') and (a2') wherein each of R.sup.1 to R.sup.7,
R.sup.12 and R.sup.13 is a hydrogen atom.
Example 30
[0183] 3.0 Gram of the CEA-1-dodecene copolymer of Synthesis
Example 3, 0.45 g of acrylic acid, 0.031 g of triphenylphosphine,
0.0070 g of hydroquinone monomethyl ether and 3.5 g of toluene were
charged and in an oil bath at 120.degree. C. the reaction was
allowed to proceed for 2 hours. From the obtained reaction
solution, toluene was distilled off at a vacuum degree of 1 Torr
and an oil bath temperature of 100.degree. C. by using a vacuum
pump to obtain a mixture containing repeating units of formulae
(a1') and (a2') wherein each of R.sup.1 to R.sup.7, R.sup.12 and
R.sup.13 is a hydrogen atom.
Example 31
[0184] 3.0 Gram of the CEA-1-octene copolymer of Synthesis Example
1, 0.665 g of methacrylic acid, 0.03 g of triphenylphosphine,
0.0074 g of hydroquinone monomethyl ether and 3.7 g of toluene were
charged and in an oil bath at 120.degree. C. the reaction was
allowed to proceed for 6 hours. From the obtained reaction
solution, toluene was distilled off at a vacuum degree of 1 Torr
and an oil bath temperature of 100.degree. C. by using a vacuum
pump to obtain a mixture containing repeating units of formulae
(a1') and (a2') wherein each of R.sup.1 to R.sup.7 and R.sup.12 is
a hydrogen atom, and R.sup.13 is a methyl group.
Example 32
[0185] 60 Gram of the CEA-1-tetradecene copolymer of Synthesis
Example 4, 18.7 g of methacrylic acid, 0.6 g of triphenylphosphine,
0.159 g of hydroquinone monomethyl ether and 79 g of ethyl acetate
were charged and in an oil bath at 100.degree. C. the reaction was
allowed to proceed for 6 hours. From the obtained reaction
solution, ethyl acetate was distilled off at a vacuum degree of 1
Torr and an oil bath temperature of 80.degree. C. by using a vacuum
pump to obtain a mixture containing repeating units of formulae
(a1') and (a2') wherein each of R.sup.1 to R.sup.7 and R.sup.12 is
a hydrogen atom, and R.sup.13 is a methyl group.
Example 33
[0186] 80.0 Gram of the CEA-1-dodecene copolymer of Synthesis
Example 5, 8.86 g of methacrylic acid, 0.8 g of triphenylphosphine,
0.18 g of hydroquinone monomethyl ether and 89 g of ethyl acetate
were charged and in an oil bath at 100.degree. C. the reaction was
allowed to proceed for 6 hours. From the obtained reaction
solution, ethyl acetate was distilled off at a vacuum degree of 1
Torr and an oil bath temperature of 80.degree. C. by using a vacuum
pump to obtain a mixture containing repeating units of formulae
(a1') and (a2') wherein each of R.sup.1 to R.sup.7 and R.sup.12 is
a hydrogen atom, and R.sup.13 is a methyl group. The viscosity
after removal by distillation was 980 mPas, and the analysis of GPC
revealed that the number average molecular weight was 1,500 and the
weight average molecular weight was 2,400.
Example 34
[0187] 25.0 Gram of the CEA-1-dodecene copolymer of Synthesis
Example 6, 6.56 g of methacrylic acid, 0.25 g of
triphenylphosphine, 0.06 g of hydroquinone monomethyl ether and 32
g of ethyl acetate were charged and in an oil bath at 100.degree.
C. the reaction was allowed to proceed for 6 hours. From the
obtained reaction solution, ethyl acetate was distilled off at a
vacuum degree of 1 Torr and an oil bath temperature of 80.degree.
C. by using a vacuum pump to obtain a mixture containing repeating
units of formulae (a1') and (a2') wherein each of R.sup.1 to
R.sup.7 and R.sup.12 is a hydrogen atom, and R.sup.13 is a methyl
group. The viscosity after removal by distillation was 4,460 mPas,
and the analysis of GPC revealed that the number average molecular
weight was 1,500 and the weight average molecular weight was
2,300.
Blending-Curing Example 1:
[0188] In a 150 mL-volume plastic vessel with a lid, 7 g of the
resin synthesized in Example 34 and 3 g of KAYARAD DPHA (a reaction
product of dipentaerythritol and acrylic acid, produced by Nippon
Kayaku Co., Ltd.) were weighed. Thereto, 0.3 g of hydroxycyclohexyl
phenyl ketone (Irgacure 184, produced by Ciba Japan) and 0.5 g of
fumed silica (AEROSIL R974, produced by Nippon Aerosil Co., Ltd.)
were added, and the mixture was kneaded in a rotation/revolution
hybrid mixer under the conditions of stirring for 5 minutes and
defoaming for 5 minutes to obtain Curable Composition A. The
composition obtained was coated by a bar coater on a polyethylene
terephthalate film (COSMOSHINE A4100, produced by Toyobo Co., Ltd.)
to a thickness of 50 .mu.m and cured by UV irradiation for 180
seconds using an UV irradiator (metal halide lamp with an output of
800 W; 17.7 mW/cm.sup.2, as the measured value by an
illuminometer).
Blending-Curing Example 2:
[0189] Gram of the resin synthesized in Example 34 and 0.2 g of
dicumyl peroxide (PERCUMYL-D, produced by NOF Corporation) were
thoroughly mixed, and the mixture was cast between two 10 cm-square
glass plates by using a 0.3 mm.phi. silicone tube as a spacer and
cured under the conditions of 100.degree. C.-1 hr, 130.degree. C.-1
hr and 160.degree. C.-1 hr.
[0190] Each of the resins synthesized in Examples 32 and 33 was
cured by the same operation according to the composition shown in
Table 3 below. The Tg and bending strength of the resulting cured
product were measured in accordance with JIS-K6911, and the results
are shown together in Table 3.
[0191] The volume shrinkage percentage was calculated by measuring
the densities before and after curing of the blend composition. The
liquid sample before curing was measured by a vibration digital
densitometer, DM-4500 (manufactured by Anton Paar). The cured
product was measured by the Archimedes method.
TABLE-US-00004 TABLE 3 Blending- Blending- Blending- Blending-
Blending- Curing Curing Curing Curing Curing Example 2 Example 3
Example 4 Example 5 Example 6 Composition Example 32 4.0 Example 33
4.0 Example 34 10.0 5.0 KAYARAD R-654 3.0 KAYARAD DPHA 2.0 5.0 2.0
ACRYESTER IBX 3.0 1.0 ACRYESTER TD 1.0 VR-77 70.0 Styrene 30.0
Dicumyl 2.0 2.0 2.0 2.0 2.0 peroxide Volume shrinkage percentage %
2.1 4.2 5.4 4.8 7.4 Bending Strength MPa 36 121 96 109 136 Elastic
680 1750 2400 2180 3450 modulus MPa Tg (glass transition 82 142 112
149 115 temperature) .degree. C. KAYARAD R-654 (produced by Nippon
Kayaku Co., Ltd.: tricyclodecanedimethylol diacrylate) KAYARAD DPHA
(produced by Nippon Kayaku Co., Ltd.: a reaction product of
dipentaerythritol and acrylic acid) ACRYESTER IBX (produced by
Mitsubishi Rayon Co., Ltd.: isobornyl methacrylate) ACRYESTER TD
(produced by Mitsubishi Rayon Co., Ltd.: tridecyl methacrylate)
VR-77 (produced by Showa Highpolymer Co., Ltd.: bisphenol-A type
epoxy acrylate)
Example 35
[0192] In a 300 mL-volume separable flask equipped with an oil bath
and a Teflon (registered trademark) stirring blade connected to a
three-one motor, 90.38 g of the CEA-4-methyl-1-pentene copolymer
synthesized in Synthesis Example 7, 21.16 g of special-grade
acrylic acid (purchased from Tokyo Chemical Industry Co., Ltd.),
1.12 g of triphenylphosphine (purchased from Tokyo Chemical
Industry Co., Ltd.) and 0.12 (g) of hydroquinone monomethyl ether
were charged. The mixture was vigorously stirred at a bath
temperature of 80 (.degree. C.) for 2 hours in a dry air atmosphere
to obtain a mixture containing repeating units of formulae (a1')
and (a2') wherein each of R.sup.1 to R.sup.7, R.sup.12 and R.sup.13
is a hydrogen atom.
Example 36
[0193] A mixture containing repeating units of formulae (a1') and
(a2') wherein each of R.sup.1 to R.sup.7, R.sup.12 and R.sup.13 is
a hydrogen atom was obtained by performing the same reaction as in
Example 35 except for changing the copolymer to 121.08 g of the
CEA-1-dodecene copolymer obtained in Synthesis Example 8.
Example 37
[0194] A mixture containing repeating units of formulae (a1') and
(a2') wherein each of R.sup.1 to R.sup.7, R.sup.12 and R.sup.13 is
a hydrogen atom was obtained by performing the same reaction as in
Example 35 except for changing the copolymer to 65.02 g of the
CEA-1-dodecene copolymer obtained in Synthesis Example 3.
Example 38
[0195] In a 150 mL-volume polyethylene vessel with a lid, 6.27 (g)
of the resin synthesized in Example 35 was weighed. Thereto, 0.63
(g) of a propylene glycol monomethyl ether acetate (produced by
Daicel Chemical Industries, Ltd.) solution of
1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, produced by Ciba
Japan) prepared to a concentration of 30 mass %, 0.32 (g) of
AEROSIL R974 (purchased from Nippon Aerosil Co., Ltd.) and 0.77 (g)
of propylene glycol monomethyl ether acetate were added, and the
mixture was stirred/defoamed in a rotation/revolution hybrid mixer
to obtain Coating Solution a. On a substrate having comb-shaped
electrodes (L/S=50/50 (.mu.m)) produced by etching a flexible
copper-lined laminated plate (trade name: UPISEL-N BE1310 (grade
name), produced by Ube Industries, Ltd.), Coating Solution a was
coated by a bar coating method to a dry thickness of 50 (.mu.m) and
then dried in a hot-air constant temperature bath at 80.degree. C.
for 5 minutes. The electrode surface was sealed with the cured
product of Coating Solution a by irradiating for 60 seconds using a
metal halide lamp-type ultraviolet irradiation apparatus (17.7
mW/cm.sup.2) to obtain Insulating Property Test Specimens a1 and
a2.
[0196] Insulating Property Test Specimen a1 was placed in a
constant-temperature/constant-humidity bath adjusted to an
atmosphere of 120.degree. C. and 95% RH, and the insulation
resistance was continuously measured by applying 100 (V) to the
electrode. The results are shown in FIG. 11.
Example 39
[0197] Coating Solution b and Insulating Property Test Specimens b1
and b2 were obtained by the same operation as in Example 38 except
for using 10.86 (g) of the resin obtained in Example 37, and the
insulation resistance was continuously measured. The results are
shown in FIG. 11.
Example 40
[0198] Insulating Property Test Specimens a2 and b2 were placed in
a constant-temperature/constant-humidity bath adjusted to
85.degree. C. and 85% RH, and the insulation resistance was
continuously measured by applying 100 (V) to the electrode. The
results are shown in FIG. 12.
Comparative Example 2
[0199] Coating Solution c and Insulating Property Test Specimens c1
and c2 were obtained in the same manner as in Example 38 except for
using a commercially available epoxy acrylate of a bisphenol A-type
epoxy resin (EBECRYL 600, produced by DAICEL-CYTEC Company
Ltd.).
[0200] Test Specimens c1 and c2 were placed in
constant-temperature/constant-humidity baths adjusted to
120.degree. C./95% RH and 85.degree. C./85% RH, respectively, and
the insulation resistance was continuously measured by applying 100
(V) to the electrode. In Test Specimen c1, the resistance value was
reduced to a value lower than 1.0.times.10.sup.6 (.OMEGA.) set as
the threshold lower limit, before the applied voltage reached the
predetermined 100 (V), and the insulating property could not be
evaluated. In Test Specimen c2, the resistance value was also
reduced in a short time to a value lower than 1.0.times.10.sup.6
(.OMEGA.) set as the threshold lower limit, and the insulation
performance was defective. The results of Test Specimen c2 are
shown in FIG. 12.
* * * * *