U.S. patent application number 17/470036 was filed with the patent office on 2021-12-30 for curable resin composition, and film, molded article, prepreg, and fiber-reinforced plastic using said curable resin composition.
This patent application is currently assigned to Mitsubishi Chemical Corporation. The applicant listed for this patent is Mitsubishi Chemical Corporation. Invention is credited to Nao DEGUCHI, Juichi FUJIMOTO, Hisaya USHIYAMA, Kenichi WATANABE.
Application Number | 20210403701 17/470036 |
Document ID | / |
Family ID | 1000005839695 |
Filed Date | 2021-12-30 |
United States Patent
Application |
20210403701 |
Kind Code |
A1 |
USHIYAMA; Hisaya ; et
al. |
December 30, 2021 |
CURABLE RESIN COMPOSITION, AND FILM, MOLDED ARTICLE, PREPREG, AND
FIBER-REINFORCED PLASTIC USING SAID CURABLE RESIN COMPOSITION
Abstract
A curable resin composition including components (A), (B), (C)
and (D) below: component (A): a bisphenol epoxy resin with a
softening point of 80.degree. C. or more, component (B): a
bisphenol epoxy resin which is liquid at 25.degree. C., component
(C): a bi- or more-functional (meth)acrylate compound, and
component (D): a curing agent.
Inventors: |
USHIYAMA; Hisaya; (Tokyo,
JP) ; DEGUCHI; Nao; (Tokyo, JP) ; WATANABE;
Kenichi; (Tokyo, JP) ; FUJIMOTO; Juichi;
(Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Mitsubishi Chemical Corporation |
Tokyo |
|
JP |
|
|
Assignee: |
Mitsubishi Chemical
Corporation
Tokyo
JP
|
Family ID: |
1000005839695 |
Appl. No.: |
17/470036 |
Filed: |
September 9, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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16447428 |
Jun 20, 2019 |
11161975 |
|
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17470036 |
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PCT/JP2017/045922 |
Dec 21, 2017 |
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16447428 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08J 5/18 20130101; C08G
59/4021 20130101; C08G 59/5033 20130101; C08G 59/5046 20130101;
C08G 59/245 20130101; C08L 33/24 20130101; C08L 63/00 20130101;
C08J 5/24 20130101 |
International
Class: |
C08L 63/00 20060101
C08L063/00; C08G 59/24 20060101 C08G059/24; C08G 59/40 20060101
C08G059/40; C08L 33/24 20060101 C08L033/24; C08G 59/50 20060101
C08G059/50; C08J 5/18 20060101 C08J005/18; C08J 5/24 20060101
C08J005/24 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 21, 2016 |
JP |
2016-247300 |
Aug 22, 2017 |
JP |
2017-159015 |
Claims
1-19. (canceled)
20. A prepreg comprising reinforcing fibers and a matrix resin,
wherein: the reinforcing fibers are impregnated with the matrix
resin, the prepreg is in the form of a sheet, and the matrix resin
is a resin composition comprising an epoxy resin and components (C)
and (D) below: component (C): a bi- or more-functional
(meth)acrylate monomer, and component (D): a curing agent
comprising at least one component (d1) selected from the group
consisting of a dicyandiamide, a urea, and an imidazole, and at
least one component (d2) which is a radical polymerization
initiator.
21. The prepreg according to claim 20, which further comprises
component (H): an oxazolidone ring-containing epoxy resin.
22. The prepreg according to claim 20, wherein the component (C)
comprises at least one monomer selected from the group consisting
of neopentyl glycol diacrylate, polyethylene glycol dimethacrylate,
trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate,
dipentaerythritol hexaacrylate, dioxane glycol diacrylate,
isocyanuric acid EO-modified di- and tri-acrylates,
2-[5-ethyl-5-[(acryloyloxy)methyl]-1,3-dioxane-2-yl]-2,2-dimethylethyl
acrylate, dimethylol-tricyclodecane diacrylate.
23. The prepreg according to claim 20, wherein the component (d2)
is at least one peroxide compound selected from the group
consisting of methyl ethyl ketone peroxide, methyl cyclohexanone
peroxide, methyl acetoacetate peroxide, acetylacetone peroxide,
1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane,
1,1-bis(t-hexylperoxy)cyclohexane,
1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane,
1,1-bis(t-butylperoxy)cyclohexane,
2,2-bis(4,4-di-t-hexylperoxycyclohexyl)propane,
1,1-bis(t-butylperoxy)cyclododecane, n-butyl
4,4-bis(t-butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane,
1,1-bis(t-butylperoxy)-2-methylcyclohexane, t-butyl hydroperoxide,
P-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide,
t-hexyl hydroperoxide, dicumyl peroxide,
2,5-dimethyl-2,5-bis(t-butyl)peroxy)hexane,
.alpha.,.alpha.'-bis(t-butylperoxy)diisopropylbenzene, t-butylcumyl
peroxide, di-t-butyl peroxide,
2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, isobutyryl peroxide,
3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl
peroxide, cinnamate peroxide, m-toluoyl peroxide, benzoyl peroxide,
diisopropyl peroxydicarbonate,
bis(4-t-butylcyclohexyl)peroxydicarbonate,
di-3-methoxybutylperoxydicarbonate,
di-2-ethylhexylperoxydicarbonate, di-sec-butylperoxydicarbonate,
di(3-methyl-3-methoxybutyl)peroxydicarbonate,
di(4-t-butylcyclohexyl)peroxydicarbonate,
.alpha.,.alpha.'-bis(neodecanoylperoxy)diisopropylbenzene,
cumylperoxyneodecanoate,
1,1,3,3-tetramethylbutylperoxyneodecanoate,
1-cyclohexyl-1-methylethylperoxyneodecanoate,
t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate,
t-hexyperoxypivalate, t-butylperoxypivalate,
2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane,
1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate,
1-cyclohexyl-1-methylperoxy-2-ethylhexanoate,
t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethyl hexanoate,
t-butylperoxyisobutyrate, t-butylperoxymaleic acid,
t-butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanoate,
t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl
monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate,
2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate,
t-hexylperoxybenzoate, t-butylperoxy-m-toluoylbenzoate,
t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate,
t-butylperoxyallyl monocarbonate, 3,3',
4,4'-tetra(t-butylperoxycarbonyl)benzophenone, di-t-hexyl peroxide,
and diisopropylbenzene hydroperoxide.
24. The prepreg according to claim 20, wherein the component (d1)
is contained in an amount of 1 to 15 parts by mass with respect to
100 parts by mass of a total of all epoxy resins contained in the
resin composition.
25. The prepreg according to claim 20, wherein the component (d2)
is contained in an amount of 0.1 to 5 parts by mass with respect to
100 parts by mass of a total of all epoxy resins and all
(meth)acrylate monomers contained in the resin composition.
26. The prepreg according to claim 20, wherein the component (C) is
contained in an amount of 5 to 45 parts by mass with respect to 100
parts by mass of a total of all epoxy resins contained in the resin
composition.
27. The prepreg according to claim 20, which further comprises
component (E): a thermoplastic resin.
28. The prepreg according to claim 27, wherein the component (E) is
contained in an amount of 1 part by mass or more and 15 parts by
mass or less with respect to 100 parts by mass of a total of all
epoxy resins contained in the resin composition.
29. The prepreg according to claim 20, wherein the component (d1)
is the dicyandiamide.
30. The prepreg according to claim 20, wherein the component (d1)
is the urea.
31. The prepreg according to claim 20, wherein the component (d1)
is the imidazole.
32. The prepreg according to claim 20, wherein the reinforcing
fibers comprise a carbon fiber.
33. A fiber-reinforced plastic molded article comprising: a matrix
resin having a sea-island structure formed from a bisphenol epoxy
resin and a (meth)acrylate; and carbon fibers, wherein the
fiber-reinforced plastic molded article has a flexural strength of
1800 MPa or more, a flexural modulus of 65 GPa or more, and an
elongation at break of 8% or more.
34. The fiber-reinforced plastic molded article according to claim
33, wherein the matrix resin comprises at least one component (d2)
which is a radical polymerization initiator.
35. The fiber-reinforced plastic molded article according to claim
34, wherein the component (d2) is at least one peroxide compound
selected from the group consisting of methyl ethyl ketone peroxide,
methyl cyclohexanone peroxide, methyl acetoacetate peroxide,
acetylacetone peroxide,
1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane,
1,1-bis(t-hexylperoxy)cyclohexane,
1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane,
1,1-bis(t-butylperoxy)cyclohexane,
2,2-bis(4,4-di-t-hexylperoxycyclohexyl)propane,
1,1-bis(t-butylperoxy)cyclododecane, n-butyl
4,4-bis(t-butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane,
1,1-bis(t-butylperoxy)-2-methylcyclohexane, t-butyl hydroperoxide,
P-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide,
t-hexyl hydroperoxide, dicumyl peroxide,
2,5-dimethyl-2,5-bis(t-butyl)peroxy)hexane,
.alpha.,.alpha.'-bis(t-butylperoxy)diisopropylbenzene, t-butylcumyl
peroxide, di-t-butyl peroxide,
2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, isobutyryl peroxide,
3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl
peroxide, cinnamate peroxide, m-toluoyl peroxide, benzoyl peroxide,
diisopropyl peroxydicarbonate,
bis(4-t-butylcyclohexyl)peroxydicarbonate,
di-3-methoxybutylperoxydicarbonate,
di-2-ethylhexylperoxydicarbonate, di-sec-butylperoxydicarbonate,
di(3-methyl-3-methoxybutyl)peroxydicarbonate,
di(4-t-butylcyclohexyl)peroxydicarbonate,
.alpha.,.alpha.'-bis(neodecanoylperoxy)diisopropylbenzene,
cumylperoxyneodecanoate,
1,1,3,3-tetramethylbutylperoxyneodecanoate,
1-cyclohexyl-1-methylethylperoxyneodecanoate,
t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate,
t-hexyperoxypivalate, t-butylperoxypivalate,
2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane,
1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate,
1-cyclohexyl-1-methylperoxy-2-ethylhexanoate,
t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethyl hexanoate,
t-butylperoxyisobutyrate, t-butylperoxymaleic acid,
t-butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanoate,
t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl
monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate,
2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate,
t-hexylperoxybenzoate, t-butylperoxy-m-toluoylbenzoate,
t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate,
t-butylperoxyallyl monocarbonate,
3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, di-t-hexyl
peroxide, and diisopropylbenzene hydroperoxide.
36. A resin composition comprising a bisphenol epoxy resin and
components (C), (D) and (H) below: component (C): a bi- or
higher-functional (meth)acrylate compound, component (D): a curing
agent, and component (H): an oxazolidone epoxy resin.
37. The resin composition according to claim 36, wherein the
bisphenol epoxy resin comprises component (A) below: component (A):
a bisphenol epoxy resin with a softening point of 80.degree. C. or
more.
38. The resin composition according to claim 36, wherein the
component (D) comprises at least one component (d1) selected from
the group consisting of a dicyandiamide, a urea, an imidazole, and
an aromatic amine, and at least one component (d2) which is a
radical polymerization initiator.
Description
[0001] This application is a continuation application of
International Application No. PCT/JP2017/045922, filed on Dec. 21,
2017, which claims the benefit of priority of the prior Japanese
Patent Application No. 2016-247300, filed on Dec. 21, 2016, and the
prior Japanese Patent Application No. 2017-159015, filed on Aug.
22, 2017, the entire contents of which are incorporated herein by
reference.
TECHNICAL FIELD
[0002] The present invention relates to a curable resin
composition, and a film, a molded article, a prepreg and a
fiber-reinforced plastic using the same, which are suitably used
for sports and leisure applications, general industrial
applications, aircraft materials applications, and the like.
BACKGROUND ART
[0003] A fiber-reinforced plastic, which is one of fiber-reinforced
composite materials, is used in wide variety of fields ranging from
sports and leisure applications to industrial applications such as
automobiles and aircrafts because of its light weight, high
strength and high rigidity.
[0004] A fiber-reinforced plastic is produced, for example, by a
method using an intermediate material, namely a prepreg in which a
reinforcing material formed of long fibers (continuous fibers) such
as reinforcing fibers, is impregnated with a matrix resin. This
method has advantages that the amount of the reinforcing fibers in
the fiber-reinforced plastic can be easily controlled, and a larger
amount of the reinforcing fibers can be incorporated into the
plastic. This method also allows the production of a molded article
by laminating a plurality of prepregs and heat-curing the laminated
prepregs.
[0005] In many cases, carbon fibers excellent in specific strength
and specific elastic modulus are used as reinforcing fibers for
meeting the needs for weight reduction, and epoxy resins excellent
in adhesiveness with carbon fibers are used as a matrix resin.
[0006] However, since epoxy resins generally tend to become brittle
when cured and have low toughness, there are technical problems
that improvements in fracture toughness and rigidity of
fiber-reinforced plastics are required. Therefore, in recent years,
it has been studied to improve toughness by adding a modifier such
as a block copolymer to utilize the phase separation structure
generated in the curing process of the resin; however, the Tg and
elastic modulus tend to decline in this modified system.
[0007] Moreover, although the toughening of the epoxy resins has
conventionally been performed by the modification methods using
engineering plastics such as a polyether sulfone, a significant
increase in viscosity is inevitable.
[0008] In order to solve this problem, it has been attempted to
simultaneously form a modifier and cure the matrix resin by
polymerizing the monomer which is the source of the modifier in the
system by the "in situ polymerization method". (Non-Patent Document
1)
[0009] In this attempt, a vinyl polymer generated by radical
polymerization is used as a modifier. Also in the field of
fiber-reinforced plastics, technological development is under way
to produce an intermediate material by using an epoxy resin and a
radical polymerization in combination (Patent Documents 1, 2 and
3).
PRIOR ART REFERENCES
Non-Patent Document
[0010] Non-Patent Document 1: Oyama Toshiyuki, Network Polymer, 36,
211 (2015)
Patent Document
[0011] Patent Document 1: Japanese Patent Granted Publication No.
3669090
[0012] Patent Document 2: Japanese Unexamined Patent Application,
First Publication No. Hei 11-43547
[0013] Patent Document 3: Japanese Patent Granted Publication No.
5424021
DISCLOSURE OF INVENTION
Problems to be Solved by the Invention
[0014] However, in none of the prior art documents, sufficient
studies are made with respect to resins for a prepreg useful for
forming a high strength and high toughness fiber-reinforced
plastic. In the composition of each of Non-Patent Document 1 and
Patent Document 3, the viscosity of the composition is too low for
use as a prepreg. The use of the composition was difficult, and the
bending strength was not sufficient. Although Patent Documents 1
and 2 recite examples using various epoxy resin compositions as a
matrix resin for a prepreg, the inventions of these patent
documents relate to prepreg production methods using the radical
polymerization as a viscosity increasing means, and the
fiber-reinforced plastics formed using the prepregs obtained by the
above methods also have insufficient bending strength.
[0015] The present invention has been made in view of the above
background, and made based on a finding that the use of a specific
epoxy resin and a radical polymerizable monomer as a matrix resin
enables the formation of a resin cured product that excels in all
of strength, elastic modulus and toughness, and the production of a
fiber-reinforced plastic having excellent mechanical properties.
The present invention provides a curable resin composition capable
of showing excellent fracture strength especially when applied to a
tubular composite material, a prepreg using the resin composition,
and a fiber-reinforced plastic formed using the prepreg.
Means to Solve the Problems
[0016] As a result of intensive studies, the present inventors have
found that the use of an epoxy resin having a specific structure
and a radically polymerizable monomer having a specific structure
can solve the above problems, and enables the production of a
fiber-reinforced plastic with desired performance.
[0017] That is, the present invention is as follows. [0018] [1] A
curable resin composition including components (A), (B), (C) and
(D) below:
[0019] component (A): a bisphenol epoxy resin with a softening
point of 80.degree. C. or more,
[0020] component (B): a bisphenol epoxy resin which is liquid at
25.degree. C.,
[0021] component (C): a bi- or more-functional (meth)acrylate
compound, and
[0022] component (D): a curing agent. [0023] [2] The curable resin
composition according to [1], which further includes component (H):
an oxazolidone ring-containing epoxy resin. [0024] [3] The curable
resin composition according to [1] or [2], wherein the component
(D) includes at least one component (d1) selected from the group
consisting of dicyandiamide, ureas, imidazoles, and aromatic
amines, and at least one component (d2) which is a radical
polymerization initiator. [0025] [4] The curable resin composition
according to [3], wherein the component (d1) is contained in an
amount of 1 to 15 parts by mass with respect to 100 parts by mass
of total of all epoxy resins contained in the curable resin
composition. [0026] [5] The curable resin composition according to
[3], wherein the component (d2) is contained in an amount of 0.1 to
5 parts by mass with respect to 100 parts by mass of total of all
epoxy resins and all (meth)acrylate compounds contained in the
curable resin composition. [0027] [6] The curable resin composition
according to any one of [1] to [5], wherein the component (A) is
contained in an amount of 20 parts by mass or more and 80 parts by
mass or less with respect to 100 parts by mass of total of all
epoxy resins contained in the curable resin composition. [0028] [7]
The curable resin composition according to any one of [1] to [6],
wherein the component (B) is contained in an amount of 20 parts by
mass or more and 80 parts by mass or less with respect to 100 parts
by mass of total of all epoxy resins contained in the curable resin
composition. [0029] [8] The curable resin composition according to
any one of [1] to [7], wherein the component (C) is contained in an
amount of 5 to 45 parts by mass with respect to 100 parts by mass
of total of all epoxy resins contained in the curable resin
composition. [0030] [9] The curable resin composition according to
any one of [1] to [8], which further includes component (E): a
thermoplastic resin. [0031] [10] The curable resin composition
according to [9], wherein the component (E) is contained in an
amount of 1 part by mass or more and 15 parts by mass or less with
respect to 100 parts by mass of total of all epoxy resins contained
in the curable resin composition. [0032] [11] A film formed from
the curable resin composition according to any one of [1] to [10].
[0033] [12] A molded article formed from the curable resin
composition according to any one of [1] to [10]. [0034] [13] A
prepreg including a mass of reinforcing fibers impregnated with the
curable resin composition of any one of [1] to [10]. [0035] [14] A
prepreg including reinforcing fibers and a matrix resin, wherein
the matrix resin is a curable resin composition comprising
components (A), (B), (C) and (D) below:
[0036] component (A): a bisphenol epoxy resin with a softening
point of 80.degree. C. or more,
[0037] component (B): a bisphenol epoxy resin which is liquid at
25.degree. C.,
[0038] component (C): a bi- or more-functional (meth)acrylate
compound, and
[0039] component (D): a curing agent. [0040] [15] The prepreg
according to [14], which further includes component (H): an
oxazolidone ring-containing epoxy resin. [0041] [16] The prepreg
according to any one of [13] to [15], which is a unidirectional
prepreg including unidirectionally aligned reinforcing fibers
impregnated with the resin composition,
[0042] wherein the prepreg has a flexural strength of 1750 MPa or
more, a flexural modulus of 125 GPa or more, and an elongation at
break of 1.2% or more, each measured with respect to a
fiber-reinforced plastic plate produced using the prepreg by a
method including cutting the prepreg in an uncured state into 24
sheets each having a size of 300 mm.times.300 mm, stacking the 24
sheets such that fiber directions of the sheets are the same to
obtain a laminate, heating the laminate in an autoclave at a
heating rate of 2.degree. C./min under a pressure of 0.04 MPa,
holding the laminate in the autoclave at 80.degree. C. for 60
minutes, heating the laminate in the autoclave at a heating rate of
2.degree. C./min under a pressure of 0.6 MPa, and holding the
laminate in the autoclave at 130.degree. C. for 90 minutes, thereby
heat-curing the laminate to obtain a fiber-reinforced plastic plate
having a thickness of 2.1 mm. [0043] [17] A fiber-reinforced
plastic comprising a cured product of the curable resin composition
according to any one of [1] to [10] and reinforcing fibers. [0044]
[18] The fiber-reinforced plastic according to [17], which is
tubular. [0045] [19] A fiber-reinforced plastic molded article
including: a matrix resin including a bisphenol epoxy resin and a
(meth)acrylate which together form a sea-island structure; and
reinforcing fibers, wherein the fiber-reinforced plastic molded
article has a flexural strength of 1800 MPa or more, a flexural
modulus of 65 GPa or more, and an elongation at break of 8% or
more.
Effect of the Invention
[0046] The curable resin composition of the present invention can
provide a cured resin with high strength, high elastic modulus and
high toughness, and the use of the curable resin composition of the
present invention as a matrix resin of a fiber-reinforced plastic
enables the production of a fiber-reinforced plastic with excellent
mechanical properties. Especially, the use of the curable resin
composition of the present invention enables the production of a
fiber-reinforced plastic tube having excellent fracture
strength.
DESCRIPTION OF THE EMBODIMENTS
[0047] Hereinbelow, the present invention will be described in
detail.
[0048] In the present invention, the term "epoxy resin" means a
compound having two or more epoxy groups in one molecule, and the
term "bi- or more-functional (meth)acrylate compound" means an
acrylate compound (acrylic ester) and/or a methacrylate compound
(methacrylic ester), each having two or more double bonds in one
molecule.
[0049] In addition, the term "curable resin composition" means a
resin composition containing an epoxy resin, a (meth)acrylate
compound, a curing agent, a curing accelerator, and optionally a
thermoplastic resin, an additive, etc.
[0050] Further, in the present invention, a cured product obtained
by curing the curable resin composition is referred to as a "cured
resin product", and a plate-shaped cured product may particularly
be referred to as a "resin plate".
[0051] In the present invention, the softening point, epoxy
equivalent and active hydrogen equivalent are values measured under
the following conditions.
[0052] 1) Softening point: value measured in accordance with
JIS-K7234: 2008 (ring and ball method).
[0053] 2) Epoxy equivalent: value measured in accordance with JIS
K-7236: 2001.
[Curable Resin Composition]
[0054] The curable resin composition of the present invention
(hereinafter also referred to as "present resin composition")
includes component (A), component (B), component (C) and component
(D). The present resin composition may further include optional
components, such as component (H), component (E), component (F),
component (G), and an additive.
<Component (A)>
[0055] The component (A) is a bisphenol epoxy resin having a
softening point of 80.degree. C. or more, preferably 82 to
150.degree. C., more preferably 85 to 145.degree. C. When the
softening point of the component (A) is not less than the above
lower limit value, a cured resin product obtainable from the
present resin composition has excellent toughness. On the other
hand, when the softening point of the component (A) is not more
than the above upper limit, it becomes likely that the heat
resistance of the cured resin product can be properly maintained,
and a prepreg excellent in tack and drape (conformability to mold
shape (flexibility)) as well as a fiber-reinforced composite
material free of voids can be obtained.
[0056] The present resin composition preferably contains the
component (A) in an amount of 20 parts by mass or more and 80 parts
by mass or less, more preferably 25 parts by mass or more and 75
parts by mass or less, and still more preferably 30 parts by mass
or more and 70 parts by mass or less, relative to 100 parts by mass
of total of all epoxy resins contained in the resin composition. In
the present specification, the total of all epoxy resins means a
total of the epoxy resins as the component (A) and the component
(B), or a total of the epoxy resins as a component (F) and/or a
component (H) to be described later as well as the component (A)
and the component (B), when the resin composition further contains
the component (F) and/or the component (H).
[0057] The lower limit of the amount of the component (A) is
preferably 25 parts by mass or more, and more preferably 30 parts
by mass or more. The upper limit of the amount of the component (A)
is preferably 75 parts by mass or less, and more preferably 70
parts by mass or less.
[0058] When the amount of the component (A) in the present resin
composition is 20 parts by mass or more, a cured resin product
excellent in toughness tends to be obtained. On the other hand,
when the amount of the component (A) is 80 parts by mass or less,
it becomes likely that the heat resistance of the cured resin
product can be properly maintained, and a prepreg excellent in tack
and drape (conformability to mold shape (flexibility)) as well as a
fiber-reinforced composite material free of voids can be
obtained.
[0059] The component (A) may be a commercially available
product.
[0060] Non-limiting examples of the commercially available
bisphenol A epoxy resins (component (A)) having a softening point
of 80.degree. C. or more include jER1055, jER1004, jER1007 and
jER1009 (each being a product name of product manufactured by
Mitsubishi Chemical Corporation); EPICLON 2050, EPICLON 3050,
EPICLON 4050, EPICLON 7050, EPICLON HM-091 and EPICLON HM-101 (each
being a product name of a product manufactured by DIC Corporation);
YD-902, YD-903N, YD-904, YD-907, YD-7910 and YD-6020 (each being a
product name of a product manufactured by Nippon Steel &
Sumikin Chemical Co., Ltd.); and the like.
[0061] Non-limiting examples of the commercially available
bisphenol F epoxy resin (component (A)) having a softening point of
80.degree. C. or more include jER4004P, jER4005P, jER4007P and
jER4010P (each being a product name of a product manufactured by
Mitsubishi Chemical Corporation); YDF2004 and YDF-2005RD (each
being a product name of a product manufactured by Nippon Steel
& Sumikin Chemical Co., Ltd.); and the like.
[0062] As the component (A), any of the above-mentioned epoxy
resins can be preferably used in the present invention, and one of
these may be used alone, or two or more may be used in
combination.
<Component (B)>
[0063] The component (B) is a bisphenol epoxy resin which is liquid
at 25.degree. C. The component (B) primarily contributes to the
improvement of the strength, elastic modulus and heat resistance of
the cured resin product obtainable from the present resin
composition. The term "liquid" above indicates that the bisphenol
epoxy resin has fluidity. The viscosity of the epoxy resin is
preferably 500 Pas or less, more preferably 0.1 to 300 Pas, at
25.degree. C. When the viscosity is in this range, the workability
of the present resin composition can be improved.
[0064] The present resin composition preferably contains the
component (B) in an amount of 20 mass parts or more and 80 mass
parts or less with respect to 100 mass parts of total of all epoxy
resins contained in the present resin composition.
[0065] The lower limit of the amount of the component (B) is more
preferably 25 parts by mass or more, still more preferably 30 parts
by mass or more. The upper limit of the amount of the component (B)
is more preferably 75 parts by mass or less, still more preferably
70 parts by mass or less.
[0066] When the amount of the component (B) is 20 parts by mass or
more in the present resin composition, a cured resin product
excellent in strength and elastic modulus is likely to be obtained.
On the other hand, when the amount of the component (B) is 80 parts
by mass or less, a cured resin product excellent in toughness is
likely to be obtained.
[0067] The component (B) may be a commercially available
product.
[0068] Non-limiting examples of the commercially available
bisphenol A epoxy resins (component (B)) which are liquid at
25.degree. C. include jER 827 (epoxy equivalent 185 g/eq) and jER
828 (epoxy equivalent 189 g/eq) (each manufactured by Mitsubishi
Chemical Corporation); YD-127 (epoxy equivalent 185 g/eq) and
YD-128 (epoxy equivalent 189 g/eq) (each manufactured by Nippon
Steel & Sumikin Chemical Co., Ltd.); EPICLON 840 (epoxy
equivalent 185 g/eq) and EPICLON 850 (epoxy equivalent 189 g/eq)
(each manufactured by DIC Corporation); D.E.R331 (epoxy equivalent
187 g/eq) and D.E.R332 (epoxy equivalent 173 g/eq) (each
manufactured by THE DOW CHEMICAL COMPANY); and the like.
[0069] Non-limiting examples of the commercially available
bisphenol F epoxy resin (component (B)) having an epoxy equivalent
of 250 or less include jER 806 (epoxy equivalent 165 g/eq) and jER
807 (epoxy equivalent 170 g/eq) (each manufactured by Mitsubishi
Chemical Corporation); YDF-170 (epoxy equivalent 170 g/eq)
(manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.);
EPICLON 830 (epoxy equivalent 170 g/eq) and EPICLON 835 (epoxy
equivalent 172 g/eq) (each manufactured by DIC Corporation);
D.E.R354 (epoxy equivalent 170 g/eq) (manufactured by THE DOW
CHEMICAL COMPANY); and the like. One of these may be used alone, or
two or more may be used in combination.
<Component (C)>
[0070] The component (C) is a bi- or more-functional (meth)acrylate
compound. The component (C) contributes to the improvement of the
strength, elastic modulus, and toughness of the cured resin product
obtainable from the present resin composition.
[0071] Examples of the bi-functional (meth)acrylate compounds
include diols such as ethylene glycol, diethylene glycol,
triethylene glycol, tetraethylene glycol, propylene glycol,
dipropylene glycol, tripropylene glycol, tetrapropylene glycol,
1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl
glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol,
1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol,
1,10-decanediol, neopentyl glycol hydroxypivalate,
tricyclodecanedimethanol, cyclohexanedimethanol, bisphenol A,
hydrogenated bisphenol A, dioxane glycol, and bisphenoxyfluorene
ethanol; and di(meth)acrylates obtained by esterification reaction
of diols (obtained by adding ethylene oxide, propylene oxide or
caprolactone to any of the above-exemplified diols) with
(meth)acrylic acid.
[0072] Examples of the tri-functional (meth)acrylate compound
include tri(meth)acrylates obtained by esterifying an alcohol
obtained by adding ethylene oxide, propylene oxide, caprolactone or
the like to triol or tetraol such as trimethylolpropane,
tris(2-hydroxyethyl) isocyanurate, glycerol, pentaerythritol, and
the like.
[0073] Examples of tetra- or more-functional (meth)acrylate
compound include poly(meth)acrylates obtained by esterifying a
polyol by reaction thereof with (meth)acrylic acid. Examples of the
polyol include ditrimethylolpropane, pentaerythritol,
dipentaerythritol, tripentaerythritol, and a polyol obtained by
adding ethylene oxide, propylene oxide or caprolactone to any of
the above-exemplified polyols.
[0074] Further examples include urethane poly(meth)acrylates
obtained by directly adding hydroxyethyl (meth)acrylate,
hydroxypropyl (meth)acrylate, pentaerythritol triacrylate or the
like to at least one kind of polyisocyanates, such as 1,3- and
1,4-diisocyanatocyclohexanes,
3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate,
4,4'-methylenedicyclohexyl diisocyanate, 2,4-methylenedicyclohexyl
diisocyanate, 2,2'-methylenedicyclohexyl diisocyanate, tolylene
diisocyanate, diphenylmethane diisocyanate, and hexamethylene
diisocyanate.
[0075] These can be used individually or in combination of two or
more thereof.
[0076] The present resin composition preferably contains the
component (C) in an amount of 5 mass parts or more and 45 mass
parts or less with respect to 100 mass parts of total of all epoxy
resins contained in the present resin composition.
[0077] The lower limit of the amount of the component (C) is more
preferably 10 parts by mass or more. The upper limit of the amount
of the component (B) is more preferably 40 parts by mass or
less.
[0078] When the amount of the component (C) is 5 parts by mass or
more in the present resin composition, a cured resin product
excellent in strength and elastic modulus is likely to be obtained.
On the other hand, when the amount of the component (C) is 45 parts
by mass or less, a cured resin product excellent in dimensional
stability is likely to be obtained.
<Component (D)>
[0079] The component (D) is a curing agent. The curing agent used
as the component (D) is not particularly limited, but it is
preferable to use, in combination, a component (d1) for curing the
components (A) and (B), and a component (d2) for curing the
component (C). As the component (d1), dicyandiamide, ureas,
imidazoles, aromatic amines, other amine-based curing agents, acid
anhydrides, boron chloride amine complex, etc. can be used, but in
particular it is preferable to use at least one curing agent
selected from dicyandiamide, ureas, imidazoles and aromatic
amines.
[0080] Dicyandiamide is preferable because it has a high melting
point and suppresses the compatibility with the epoxy resin in a
low temperature range, so that a curable resin composition having
excellent pot life is likely to be obtained as a result of the use
thereof as the curing agent (d1). Further, the use of dicyandiamide
as the curing agent (d1) is preferable also in that the presence of
dicyandiamide as the curing agent (d1) in the curable resin
composition tends to improve the mechanical properties of the cured
resin product.
[0081] With respect to the amount of dicyandiamide in the curable
resin composition of the present invention, the amount is
preferably such that the number of moles of active hydrogen of
dicyandiamide is preferably 0.4 to 1 times the total number of
moles of epoxy groups possessed by the epoxy resins contained in
the curable resin composition. When it is 0.4 times or more, a
cured product having good heat resistance and good mechanical
properties (that is, high strength and elastic modulus) tends to be
obtained. Further, with this number being 1 times or less, there is
an advantage that a cured product having good mechanical properties
(that is, excellent plastic deformation capacity and impact
resistance) tends to be obtained. Furthermore, this number of moles
of active hydrogen of dicyandiamide is more preferably 0.5 to 0.8
times since the cured resin product tends to excel more in heat
resistance.
[0082] Non-limiting examples of commercially available products of
dicyandiamide include DICY7 and DICY15 (each manufactured by
Mitsubishi Chemical Corporation); DICYANEX1400F (manufactured by
Air Products and Chemicals Inc.); and the like.
[0083] With respect to the urea usable as the component (d1), there
is no particular limitation as long as it has a dimethylureido
group in its molecule, and generates an isocyanate group and
dimethylamine when heated at high temperature, which activate epoxy
groups of the component (A) and the component (B) or other epoxy
resins to be used in combination. Examples of the ureas include an
aromatic dimethylurea having a dimethylureido group bonded to its
aromatic ring, and an aliphatic dimethyl urea having a
dimethylureido group bonded to an aliphatic compound. Among these,
an aromatic dimethyl urea is preferable in that the curing speed is
increased and the heat resistance and flexural strength of the
cured product tend to improve.
[0084] As the aromatic dimethyl urea, for example,
phenyldimethylurea, methylene bis(phenyldimethylurea), and tolylene
bis(dimethylurea) can be suitably used. Specific examples thereof
include 4,4'-methylenebis (phenyldimethylurea) (MBPDMU),
3-phenyl-1,1-dimethylurea (PDMU),
3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU),
3-(3-chloro-4-methylphenyl)-1,1-dimethylurea,
2,4-bis(3,3-dimethylureido) toluene (TBDMU), and dimethylurea
obtained from m-xylylene diisocyanate and dimethylamine. Among
these, DCMU, MBPDMU, TBDMU, and PDMU are more preferable in terms
of the abilities to accelerate curing and impart heat resistance to
a cured resin product.
[0085] One of these may be used alone, or two or more of these may
be used in combination.
[0086] Examples of the aliphatic dimethylurea include dimethylurea
obtained from isophorone diisocyanate and dimethylamine, and
dimethylurea obtained from hexamethylene diisocyanate and
dimethylamine.
[0087] The ureas may be commercially available products.
[0088] Non-limiting examples of the commercial products of DCMU
include DCMU-99 (manufactured by Hodogaya Chemical Industry Co.,
Ltd.) and the like.
[0089] Non-limiting examples of the commercial products of MBPDMU
include Technicure MDU-11 (manufactured by A & C Catalysts
Inc.), Omicure 52 (manufactured by PTI Japan, Ltd.) and the
like.
[0090] Non-limiting examples of the commercial products of PDMU
include Omicure 94 (manufactured by PTI Japan, Ltd.) and the
like.
[0091] Non-limiting examples of the commercial products of TBDMU
include Omicure 24 (manufactured by PTI Japan, Ltd.),
[0092] U-CAT 3512T (manufactured by San-Apro Ltd.) and the
like.
[0093] Non-limiting examples of the commercial products of
aliphatic dimethylurea include U-CAT 3513N (manufactured by
San-Apro Ltd.) and the like.
[0094] The amount of the urea is preferably 1 to 15 parts by mass,
more preferably 2 to 10 parts by mass, with respect to 100 parts by
mass of total of all epoxy resins contained in the curable resin
composition of the present invention. When the amount of the ureas
is 1 part by mass or more, the urea sufficiently cures and
accelerates the curing of the epoxy resins contained in the epoxy
resin composition, whereby mechanical properties and heat
resistance are likely to improve. On the other hand, when the
amount of the urea is 15 parts by mass or less, the toughness of
the cured resin product is likely to be maintained high.
[0095] The imidazoles usable as the component (d1) may be
imidazoles, or may be imidazole adducts, imidazole clathrates,
microencapsulated imidazoles or imidazole compounds stabilized by
coordination with a stabilizer.
[0096] Each of these compounds has a nitrogen atom having an
unshared electron pair in its structure, which can activate the
epoxy groups of the component (A) or the component (B), or also
activate the other epoxy resins to be used, to thereby accelerate
the curing.
[0097] Non-limiting specific examples of the imidazole include
2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole,
2-heptadecylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole and
2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole,
1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole,
1-cyanoethyl-2-ethyl-4-methylimidazole,
1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole,
1-cyanoethyl-2-ethyl-4-methylimidazolium trimellitate,
1-cyanoethyl-2-undecylimidazolium trimellitate,
1-cyanoethyl-2-phenylimidazolium trimellitate,
2,4-diamino-6-(2'-methylimidazolyl-(1'))ethyl-s-triazine,
2,4-diamino-6-(2'-undecylimidazolyl-(1'))-ethyl-s-triazine,
2,4-diamino-6-(2'-ethyl-4-methylimidazolyl-(1'))-ethyl-s-triazine,
2,4-diamino-6-(2'-methylimidazolyl-(1')-ethyl
-s-triazine-isocyanuric acid adduct, 2-phenylimidazole-isocyanuric
acid adduct, 2-methylimidazole-isocyanuric acid adduct,
1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy) methylimidazole,
2-phenyl-4,5-dihydroxymethylimidazole,
2-phenyl-4-methyl-5-hydroxymethyl imidazole, and the like.
[0098] The imidazole adducts, imidazole clathrates including other
molecules, microencapsulated imidazoles and imidazole compounds
coordinated with a stabilizer are modified products of the
imidazole described above. The adduct treatment, clathration with
other molecules, microencapsulation and coordination with a
stabilizer can decrease the activity of the imidazole, which allows
the curable resin composition to exhibit excellent pot life in a
low temperature range while exhibiting high capability of curing or
cure acceleration.
[0099] The imidazoles may be commercially available products.
[0100] Non-limiting examples of the commercial products of
imidazole include 2E4MZ, 2P4MZ, 2PZ-CN , C11Z-CNS, C11Z-A, 2MZA-PW,
2MA-OK, 2P4MHZ-PW and 2PHZ-PW (each manufactured by Shikoku
Chemicals Corporation).
[0101] Non-limiting examples of the commercial products of
imidazole adducts include PN-50, PN-50J, PN-40, PN-40J, PN-31,
PN-23 and PN-H, all of which have a structure formed by
ring-opening addition of an imidazole compound to epoxy groups of
an epoxy resin (each manufactured by Ajinomoto Fine-Techno Co.,
Inc.).
[0102] Non-limiting examples of the commercial products of
imidazole clathrates include TIC-188, KM-188, HIPA-2P4MHZ,
NIPA-2P4MHZ, TEP-2E4MZ, HIPA-2E4MZ and NIPA-2E4MZ (each
manufactured by Nippon Soda Co., Ltd.).
[0103] Non-limiting examples of the commercial products of
microencapsulated imidazoles include Novacure HX3721, HX3722,
HX3742 and HX3748 (each manufactured by Asahi Kasei E-materials
Corp.); and LC-80 (manufactured by A & C Catalysts Inc.).
[0104] As for the imidazole compounds coordinated with a
stabilizer, for example, such compounds can be prepared by
combining Cureduct P-0505 (bisphenol A diglycidyl
ether/2-ethyl-4-methylimidazole adduct), which is an imidazole
adduct manufactured by Shikoku Chemicals Corporation, with L-07N
(epoxy-phenol-borate blend), which is a stabilizer manufactured by
Shikoku Chemicals Corporation. Similar effects can be obtained by
using the aforementioned various imidazoles and imidazole compounds
such as imidazole adducts instead of the aforementioned Cureduct
P-0505. As an imidazole compound before being coordinated with a
stabilizer, any of those showing low solubility with respect to an
epoxy resin can be suitably used, and Cureduct P-0505 is preferable
from this point of view.
[0105] The amount of the imidazole is preferably 1 to 15 parts by
mass, more preferably 2 to 10 parts by mass, with respect to 100
parts by mass of total of all epoxy resins contained in the curable
resin composition of the present invention. When the amount of the
imidazole is 1 part by mass or more, the imidazole is likely to
sufficiently cure and accelerate the curing of the epoxy resins
contained in the epoxy resin composition, and a sufficiently high
heat resistance is likely to be achieved. On the other hand, when
the amount of the imidazole is 15 parts by mass or less, a cured
resin product having excellent mechanical properties is likely to
be obtained.
[0106] Non-limiting examples of the aromatic amines usable as the
component (d1) include
3,3'-diisopropyl-4,4'-diaminodiphenylmethane,
3,3'-di-t-butyl-4,4'-diaminodiphenylmethane,
3,3'-diethyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane,
3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane,
3,3'-di-t-butyl-5,5'-dimethyl -4,4'-diaminodiphenylmethane, 3,3',
5,5'-tetraethyl-4,4'-diaminodiphenylmethane,
3,3'-diisopropyl-5,5'-diethyl-4,4'-diaminodiphenylmethane,
3,3'-di-t-butyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3',
5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane,
3,3'-di-t-butyl-5,5'-diisopropyl-4,4'-diaminodiphenylmethane, 3,3',
5,5'-tetra-t-butyl-4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone,
3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine,
diethyltoluenediamine and the like. Among these, it is preferable
to use 4,4'-diaminodiphenylsulfone and 3,3'-diaminodiphenylsulfone
because these are excellent in heat resistance and elastic modulus
and can provide a cured product which has a small linear expansion
coefficient and suffers less reduction of heat resistance due to
moisture absorption. 4,4'-diaminodiphenylsulfone is also preferable
in that the tack life of the prepreg can be maintained for a long
period of time. 3,3'-diaminodiphenylsulfone is inferior to
4,4'-diaminodiphenylsulfone in the tack life of the prepreg and the
heat resistance of the cured product; nevertheless,
3,3'-diaminodiphenylsulfone is preferable because it can increase
the elastic modulus and toughness of the cured product. Further, it
is preferable to blend 4,4'-diaminodiphenylsulfone together with
3,3'-diaminodiphenylsulfone because the heat resistance and elastic
modulus of the cured product can be easily adjusted. These aromatic
amines may be used alone or in combination as appropriate.
[0107] As for the blending amount of the aromatic amines,
especially in the case of diaminodiphenylsulfone, the active
hydrogen equivalent number of the amino group is preferably 0.5 to
1.5 times, more preferably 0.6 to 1.4 times the epoxy equivalent
number of all epoxy resins contained in the curable resin
composition of the present invention. By blending such epoxy resin
curing agents in an amount of 0.5 to 1.5 times, the elastic
modulus, toughness and heat resistance of the cured resin product
are likely to fall within favorable ranges.
[0108] The aromatic amines may be commercially available
products.
[0109] Non-limiting examples of commercial products of
4,4'-diaminodiphenyl sulfone include Seikacure S (active hydrogen
equivalent 62 g/eq, manufactured by Wakayama Seika Kogyo Co.,
Ltd.), and Sumicure S (active hydrogen equivalent 62 g/eq,
manufactured by Sumitomo Chemical Co., Ltd.). Non-limiting examples
of commercial products of 3,3'-diaminodiphenyl sulfone include
3,3'-DAS (active hydrogen equivalent 62 g/eq, manufactured by
Mitsui Fine Chemicals, Inc.).
[0110] Non-limiting examples of other commercial products of the
aromatic amines include MDA-220 (active hydrogen equivalent 50
g/eq, manufactured by Mitsui Chemicals Inc.); "jER Cure (registered
trademark)" W (active hydrogen equivalent 45 g/eq, Japan Epoxy
Resin Co., Ltd.); and "Lonzacure (registered trademark)" M-DEA
(active hydrogen equivalent 78 g/eq), "Lonzacure (registered
trademark" M-DIPA (active hydrogen equivalent 92 g/eq), "Lonzacure
(registered trademark)" M-MIPA (active hydrogen equivalent 78
g/eq), and "Lonzacure (registered trademark)" DETDA 80 (active
hydrogen equivalent 45 g/eq) (each manufactured by Lonza,
Inc.).
[0111] Examples of the other amine-based curing agent that can be
used as component (d1) include metaphenylene diamine,
diaminodiphenylmethane, metaxylene diamine, isophorone diamine,
triethylenetetramine and the like.
[0112] Further, examples of the acid anhydride that can be used as
component (d1) include hydrogenated methyl nadic anhydride, methyl
hexahydrophthalic anhydride and the like.
[0113] As the radical polymerization initiator which can be used as
the component (d2), azo compounds, peroxide compounds, photo
radical polymerization initiators and the like can be mentioned. In
particular, it is preferable to use at least one curing agent
selected from peroxide compounds.
[0114] Examples of the azo compounds include
2,2-azobis(isobutyronitrile),
2,2-azobis(2,4-dimethylvaleronitrile), dimethyl
2,2-azobis(2-methylpropionate), 2,2-azobis(2-methylbutyronitrile),
1,1-azobis(cyclohexane-1-carbonitrile), 2,2-azobis(N
-butyl-2-methylpropionamide), dimethyl
1,1-azobis(1-cyclohexanecarboxylate) and the like.
[0115] Examples of the peroxide compounds include methyl ethyl
ketone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate
peroxide, acetylacetone peroxide,
1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane,
1,1-bis(t-hexylperoxy)cyclohexane,
1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane,
1,1-bis(t-butylperoxy)cyclohexane,
2,2-bis(4,4-di-t-hexylperoxycyclohexyl)propane,
1,1-bis(t-butylperoxy)cyclododecane, n-butyl
4,4-bis(t-butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane, 1
1-bis(t-butylperoxy)-2-methylcyclohexane, t-butyl hydroperoxide,
P-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide,
t-hexyl hydroperoxide, dicumyl peroxide,
2,5-dimethyl-2,5-bis(t-butyl)peroxy)hexane,
.alpha.,.alpha.'-bis(t-butylperoxy)diisopropylbenzene, t-butylcumyl
peroxide, di-t-butyl peroxide,
2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, isobutyryl peroxide,
3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl
peroxide, cinnamate peroxide, m-toluoyl peroxide, benzoyl peroxide,
diisopropyl peroxydicarbonate,
bis(4-t-butylcyclohexyl)peroxydicarbonate,
di-3-methoxybutylperoxydicarbonate,
di-2-ethylhexylperoxydicarbonate, di-sec-butylperoxydicarbonate,
di(3-methyl-3-methoxybutyl)peroxydicarbonate,
di(4-t-butylcyclohexyl)peroxydicarbonate,
.alpha.,.alpha.'-bis(neodecanoylperoxy)diisopropylbenzene,
cumylperoxyneodecanoate,
1,1,3,3-tetramethylbutylperoxyneodecanoate,
1-cyclohexyl-1-methylethylperoxyneodecanoate,
t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate,
t-hexyperoxypivalate, t-butylperoxypivalate,
2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane,
1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate,
1-cyclohexyl-1-methylperoxy-2-ethylhexanoate,
t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethyl hexanoate,
t-butylperoxyisobutyrate, t-butylperoxymaleic acid,
t-butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanoate,
t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl
monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate,
2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate,
t-hexylperoxybenzoate, t-butylperoxy-m-toluoylbenzoate,
t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate,
t-butylperoxyallyl monocarbonate,
3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, dibenzoyl
peroxide, di-t-hexyl peroxide, diisopropylbenzene hydroperoxide,
and the like.
[0116] Examples of the radical photopolymerization initiator
include benzophenone, 4,4-bis(diethylamino)benzophenone,
2,4,6-trimethylbenzophenone, methyl o-benzoylbenzoate,
4-phenylbenzophenone,
2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl]-2-methylpr-
opan-1-one, t-butylanthraquinone, 2-ethylanthraquinone,
diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one,
benzyldimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, benzoin
methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin
isobutyl ether,
2-methyl-4-(methylthio)phenyl]-2-morpholino-1-propanone,
2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,
diethylthioxanthone, isopropylthioxanthone,
2,4,6-trimethylbenzoyldiphenylphosphine oxide,
bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide,
bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, methyl benzoyl
formate, and the like.
[0117] The above compounds can be used alone or in combination of
two or more as the component (d2), but in terms of storage
stability of the prepreg, those having a 10-hour half-life
temperature of 100.degree. C. or higher are preferable.
[0118] The amount of component (d2) is preferably 0.1 to 5 parts by
mass, more preferably 0.2 to 3 parts by mass, with respect to 100
parts by mass of total of all epoxy resins and all (meth)acrylate
compounds contained in the curable resin composition of the present
invention. When the amount of the component (d2) is 0.1 parts by
mass or more, the (meth)acrylate compounds contained in the curable
resin composition are likely to be sufficiently cured. On the other
hand, when the amount of the component (d2) is 5 parts by mass or
less, a resin composition having excellent storage stability is
likely to be obtained.
[0119] In the present specification, the term "all (meth)acrylate
compounds" means the (meth)acrylate compounds as the component (C),
or total of the (meth)acrylate compounds as the component (C) and
component (G) (to be described later) when the curable resin
composition of the present invention further contains the component
(G).
<Component (E)>
[0120] The thermoplastic resin may be, if necessary, blended into
the curable resin composition of the present invention as a
component (E) for the purpose of controlling resin flow during
molding of the curable resin composition and imparting toughness to
a resulting cured resin product. That is, the present resin
composition preferably further contains a thermoplastic resin as
the component (E).
[0121] The present resin composition preferably contains the
component (E) in an amount of 1 part by mass or more and 15 parts
by mass or less, preferably 2 parts by mass or more and 10 parts by
mass or less, with respect to 100 parts by mass of total of all
epoxy resins contained in the present resin composition.
[0122] When the amount of the component (E) is 1 part by mass or
more, sufficient effects of resin flow control and
physical-property improvement are likely to be achieved, which is
favorable. On the other hand, when the amount of the component (E)
is 15 parts by mass or less, the viscosity of the curable resin
composition, the heat resistance and mechanical properties of the
cured resin product, and the tack and drape of the prepreg are
likely to be sufficiently maintained, which is favorable.
[0123] Non-limiting examples of the thermoplastic resin include
polyamide, polyester, polycarbonate, polyether sulfone,
polyphenylene ether, polyphenylene sulfide, polyetheretherketone,
polyetherketone, polyimide, polytetrafluoroethylene, polyether,
polyolefin, liquid crystal polymer, polyarylate, polysulfone,
polyacrylonitrile styrene, polystyrene, polyacrylonitrile,
polymethyl methacrylate, ABS (acrylonitrile-butadiene-styrene
copolymer), AES (acrylonitrile-ethylene-propylene rubber-styrene
copolymer), ASA (acrylonitrile-acrylate rubber-styrene copolymer),
polyvinyl chloride, polyvinyl formal resin, phenoxy resin, and
block polymers.
[0124] Among these, phenoxy resin, polyether sulfone and polyvinyl
formal resin are preferable because they are excellent in resin
flow controllability and the like. Also, the phenoxy resin and the
polyether sulfone are preferable from the viewpoint of further
improving the heat resistance and flame retardancy of the cured
resin product, and the polyvinyl formal resin is preferable from
the viewpoint of ease in controlling the tack of the obtained
prepreg within an appropriate range without deteriorating the heat
resistance of the cured product and improving the adhesion between
the reinforcing fibers and the epoxy resin composition. The block
polymers are preferable because they improve toughness and impact
resistance.
[0125] One of these thermoplastic resins may be used alone, or two
or more thereof may be used in combination.
[0126] Non-limiting examples of the phenoxy resin include YP-50,
YP-50S, YP70, ZX-1356-2, and FX-316 (each manufactured by Nippon
Steel & Sumikin Chemical Co., Ltd.).
[0127] Non-limiting examples of the polyvinyl formal resin include
Vinylec (registered trademark) K (mass average molecular weight:
59,000), Vinylec L (mass average molecular weight: 66,000), Vinylec
H (mass average molecular weight: 73,000), and Vinylec E (mass
average molecular weight: 126,000), all of which are manufactured
by JNC Corporation.
[0128] Further, when the cured resin product is required to have
heat resistance at a temperature exceeding 180.degree. C.,
polyether sulfone and polyether imide are preferably used. Specific
examples of the polyether sulfone include Sumika Excel (registered
trademark) 3600P (weight average molecular weight: 16,400), Sumika
Excel 5003 P (mass average molecular weight: 30,000), Sumika Excel
5200 P (mass average molecular weight: 35,000), and Sumika Excel
7600P (mass average molecular weight: 45,300), all of which are
manufactured by Sumitomo Chemical Co., Ltd.
[0129] Non-limiting examples of the polyether imide include ULTEM
1000 (mass average molecular weight: 32,000), ULTEM 1010 (mass
average molecular weight: 32,000), and ULTEM 1040 (mass average
molecular weight: 20,000), all of which are manufactured by SABIC
Innovative Plastics Co., Ltd.
[0130] Non-limiting examples of the block copolymers include
Nanostrength M52, Nanostrength M52N, Nanostrength M22, Nanostrength
M22N, Nanostrength 123, Nanostrength 250, Nanostrength 012,
Nanostrength E20, and Nanostrength E40, which are manufactured by
ARKEMA; and TPAE-23, TPAE-31, TPAE-38, TPAE-63, TPAE-100, and
PA-260, which are manufactured by T & K TOKA Corporation.
[0131] For the purpose of adjusting the viscoelasticity of the
present resin composition in an uncured state to improve the
workability and improving the strength, elastic modulus, toughness
and heat resistance of the cured resin product, the present resin
composition may include the epoxy resins described below as a
component (F).
[0132] The component (F) is not particularly limited as long as it
is an epoxy resin other than the bisphenol epoxy resins used as the
component (A) and the component (B) and is suitable for the above
purposes, but bi- or more-functional epoxy resins are preferably
used. Examples of such epoxy resins include bisphenol S epoxy
resins, bisphenol E epoxy resins, bisphenol Z epoxy resins,
bisphenol AD epoxy resins, bisphenol epoxy resins other than those
used as the component (A) or the component (B), biphenyl epoxy
resins, naphthalene epoxy resins, dicyclopentadiene epoxy resins,
phenol novolac epoxy resins, cresol novolac epoxy resins,
trisphenol methane epoxy resins, glycidyl amine epoxy resins such
as tetraglycidyldiaminodiphenylmethane and triglycidylaminophenol;
glycidyl ether epoxy resins other than mentioned above, such as
tetrakis(glycidyloxyphenyl)ethane and tris(glycidyloxy)methane,
epoxy resins as modified products of those exemplified above,
phenol aralkyl epoxy resins, and the like.
[0133] A tri- or more-functional epoxy resin can provide more
excellent strength, elastic modulus, and heat resistance.
Therefore, it is preferable to use triglycidyl para- or
meta-aminophenol epoxy resins, tetraglycidyl diaminodiphenylmethane
epoxy resins, phenol novolac epoxy resins, and cresol novolac epoxy
resins.
[0134] Non-limiting examples of the commercially available epoxy
resins usable as the component (F) include jER1001 (epoxy
equivalent 475 g/eq), jER 1002 (epoxy equivalent 650 g/eq), jER 604
(epoxy equivalent 120 g/eq), jER 630 (epoxy equivalent 98 g/eq),
jER1032H60 (epoxy equivalent 169 g/eq), jER 152 (epoxy equivalent
175 g/eq), jER 154 (epoxy equivalent 178 g/eq), YX-7700 (epoxy
equivalent 273 g/eq), and YX-4000 (epoxy equivalent 186 g/eq) (each
manufactured by Mitsubishi Chemical Corporation); GAN (epoxy
equivalent: 125 g/eq), GOT (epoxy equivalent: 135 g/eq), NC-2000
(epoxy equivalent: 241 g/eq), and NC-3000 (epoxy equivalent: 275
g/eq) (each manufactured by Nippon Kayaku Co.,Ltd.); YDPN-638
(epoxy equivalent 180 g/eq), and TX-0911 (epoxy equivalent 172
g/eq) (each manufactured by Nippon Steel & Sumikin Chemical
Co., Ltd.); Epon 165 (epoxy equivalent 230 g/eq) (manufactured by
Momentive Specialty Chemicals Inc.); MY-0500 (epoxy equivalent 110
g/eq), MY-0600 (epoxy equivalent 106 g/eq), and ECN-1299 (epoxy
equivalent 230 g/eq) (each manufactured by Huntsman Japan K.K.);
HP-4032 (epoxy equivalent 150 g/eq), HP-4700 (epoxy equivalent 162
g/eq), HP-7200 (epoxy equivalent 265 g/eq), and TSR-400 (each
manufactured by DIC Corporation); AER 4152, AER 4151, LSA 3301, and
SA2102 (each manufactured by Asahi Kasei E-materials Corp.);
ACR1348 (epoxy equivalent 350 g/eq) (manufactured by Adeka
Corporation); DER 852 (epoxy equivalent 320 g/eq), and DER 858
(epoxy equivalent 400 g/eq) (each manufactured by THE DOW CHEMICAL
COMPANY); and the like.
[0135] The amount of component (F) is preferably 5 to 35 parts by
mass, more preferably 10 to 30 parts by mass, with respect to 100
parts by mass of total of all epoxy resins contained in the curable
resin composition of the present invention. When the amount of the
component (F) is 5 mass parts or more, a sufficient
physical-property improvement effect is likely to be achieved,
which is favorable. On the other hand, when the amount of the
component (F) is 35 mass parts or less, the characteristics of the
curable resin composition of the present invention are likely to be
satisfactorily maintained, which is favorable.
[0136] The present resin composition may contain, as a component
(G), the following monofunctional (meth)acrylate compounds for the
purpose of controlling the cross-linked structure of the present
resin composition, reducing the viscosity, and imparting
adhesiveness. The term "monofunctional (meth)acrylate compounds"
means acrylate compounds and/or methacrylate compounds having one
double bond in one molecule.
[0137] Specific examples of compounds that can be used as the
component (G) include (meth)acrylates, such as 2-hydroxyethyl
(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl
(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl
(meth)acrylate, cyclohexyl (meth)acrylate, isobornyl
(meth)acrylate, norbornyl (meth)acrylate,
2-(meth)acryloyloxymethyl-2-methylbicycloheptane, adamantyl
(meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate,
dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate,
tetracyclododecanyl (meth)acrylate, cyclohexanedimethanol mono
(meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl
(meth)acrylate, methoxytriethylene glycol (meth)acrylate,
butoxyethyl (meth)acrylate, methoxydipropylene glycol
(meth)acrylate, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane,
4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane,
o-phenylphenol (meth)acrylate, ethoxylated o-phenylphenol
(meth)acrylate, N-(meth) acryloyloxyethyl hexahydrophthalimide,
paracumyl phenol (meth)acrylate, ethoxylated paracumyl phenol
(meth)acrylate, and trimethylolpropane formal (meth)acrylate; vinyl
ester monomers such as vinyl acetate, vinyl butyrate,
N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone,
N-vinylcaprolactam, and divinyl adipate; vinyl ethers, such as
ethyl vinyl ether, and phenyl vinyl ether; and acrylamides, such as
acrylamide, N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide,
N-methylol acrylamide, N-methoxymethyl acrylamide, N-butoxymethyl
acrylamide, N-t-butyl acrylamide, acryloyl morpholine, hydroxyethyl
acrylamide, and methylene bisacrylamide.
[0138] One of these may be used alone, or two or more of these may
be used in combination.
[0139] Among these, a compound having a cyclic structure in its
molecule is preferable because the cure shrinkage of the
composition to be obtained is low and the strength of the resulting
cured product is excellent.
[0140] In the present invention, the amount of the component (G) is
not particularly limited, but is preferably in the range of 0.1 to
5 parts by mass with respect to 100 parts by mass of total of all
epoxy resins contained in the present resin composition. If the
amount of the component (G) is 0.1 mass part or more, a sufficient
physical-property improvement effect is likely to be achieved,
which is favorable. On the other hand, when the amount of the
component (G) is 5 mass parts or less, the characteristics of the
curable resin composition of the present invention are likely to be
satisfactorily maintained, which is favorable.
<Component (H)>
[0141] The component (H) is an oxazolidone ring-containing epoxy
resin.
[0142] The oxazolidone ring-containing epoxy resin is an epoxy
resin having an oxazolidone ring structure, which improves the
workability at normal temperature of a prepreg containing the epoxy
resin composition containing the oxazolidone ring-containing epoxy
resin, and also improves the elastic modulus and heat resistance of
the cured product of the epoxy resin composition as well as the
adhesion thereof with reinforcing fibers.
[0143] An oxazolidone-ring structure is generated through addition
reaction of an isocyanate group and an epoxy group. The method for
producing the oxazolidone skeleton-containing epoxy resin in the
present invention is not particularly limited. For example, the
oxazolidone skeleton-containing epoxy resin can be obtained in an
approximately theoretical amount by reacting an isocyanate compound
and an epoxy resin having a biphenyl skeleton in the presence of an
oxazolidone ring formation catalyst. The isocyanate compound and
the epoxy resin are preferably reacted with an equivalent ratio in
a range of 1:2 to 1:10. When the ratio is within the above range,
the cured product of the epoxy resin is likely to have further
improved heat resistance and water resistance. In the present
invention, various isocyanate compounds can be used as raw
materials, but in order to incorporate the oxazolidone ring
structure into the skeleton of the epoxy resin, it is preferable to
use an isocyanate compound having a plurality of isocyanate groups.
Moreover, for imparting higher heat resistance to the cured product
of the epoxy resin composition containing the component (H), it is
preferable to use a diisocyanate which has a rigid structure.
[0144] Non-limiting specific examples of the isocyanate compound
usable as a raw material include bifunctional isocyanate compounds
such as methane diisocyanate, butane-1,1-diisocyanate,
ethane-1,2-diisocyanate, butane-1,2-diisocyanate, transvinylidene
diisocyanate, propane-1,3-diisocyanate, butane-1,4-diisocyanate,
2-butene-1,4-diisocyanate, 2-methylbutene-1,4-diisocyanate,
2-methylbutane-1,4-diisocyanate, pentane-1,5-diisocyanate
2,2-dimethylpentane-1,5-diisocyanate, hexane -1,6-diisocyanate,
heptane-1,7-diisocyanate, octane-1,8-diisocyanate,
nonane-1,9-diisocyanate, decane-1,10-isocyanate, dimethylsilane
diisocyanate, diphenylsilane diisocyanate,
.omega.,.omega.'-1,3-dimethylbenzene diisocyanate,
.omega.,.omega.'-1,4-dimethylbenzene diisocyanate,
.omega.,.omega.'-1,3-dimethylcyclohexane diisocyanate,
.omega.,.omega.'-1,4-dimethylcyclohexane diisocyanate,
.omega.,.omega.'-1,4-dimethylnaphthalene diisocyanate,
.omega.,.omega.'-1,5-dimethylnaphthalene diisocyanate,
cyclohexane-1,3-diisocyanate, cyclohexane-1, 4-diisocyanate,
3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate,
dicyclohexylmethane-4,4'-diisocyanate, 1,3-phenylene diisocyanate,
1,4-phenyne diisocyanate, 1-methylbenzene-2,4-diisocyanate,
1-methylbenzene-2,5-diisocyanate, 1-methylbenzene-2,6-diisocyanate,
1-methylbenzene-3,5-diisocyanate, diphenyl ether-4,
4'-diisocyanate, diphenylether-2,4'-diisocyanate,
naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate,
biphenyl-4,4'-diisocyanate,
3,3'-dimethylbiphenyl-4,4'-diisocyanate,
2,3'-dimethoxybisphenyl-4,4'-diisocyanate,
diphenylmethane-4,4'-diisocyanate,
3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate,
4,4'-dimethoydiphenylmethane-3,3'-diisocyanate, norbornene
diisocyanate, diphenylsulfite-4,4'-diisocyanate, and
diphenylsulfone-4,4'-diisocyanate; multifunctional isocyanate
compounds such as polymethylene polyphenyl isocyanate,
triphenylmethane triisocyanate, and tris(4-phenylisocyanate
thiophosphate)-3,3',4,4'-diphenyl methane tetraisocyanate;
multimers such as dimers and trimers of the above-mentioned
isocyanate compounds; blocked isocyanates masked by an alcohol or
phenol, and bisurethane compounds; and the like. These isocyanate
compounds may be used in combination of two or more thereof.
[0145] Among the above-mentioned isocyanate compounds, from the
viewpoint of tendency of improving heat resistance, preferred are
bifunctional or trifunctional isocyanate compounds, more preferred
are bifunctional isocyanate compounds, still more preferred are
bifunctional isocyanate compounds having a skeleton selected from
isophorone, benzene, toluene, diphenylmethane, naphthalene,
norbornene, polymethylene polyphenylene polyphenyl and
hexamethylene. When the number of functional groups of the
isocyanate compound is too large, the storage stability of the
epoxy resin composition tends to decrease. When the number of
functional groups is too small, the heat resistance of the cured
product obtainable from the epoxy resin composition tends to
decrease.
[0146] Further, as the epoxy resin used as the raw material of the
component (H), various epoxy resins can be used. However, for
efficiently incorporating an oxazolidone ring structure into the
skeleton of an epoxy resin, it is preferable to use an epoxy resin
having epoxy groups at both terminals of its molecule. Non-limiting
specific examples of the epoxy resin usable as the raw material of
the component (H) include epoxy resins derived from dihydric
phenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol
S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl
bisphenol AD, tetramethylbisphenol S and tetrabromobisphenol A;
epoxy resins derived from tris(glycidyloxyphenyl)alkanes such as
1,1,1-tris(4-hydroxyphenyl)methane, and
1,1,1-(4-hydroxyphenyl)ethane,
4,4-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol;
and epoxy resins derived from novolak, such as phenol novolac,
cresol novolak, and bisphenol A novolak. As the epoxy resin,
bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl epoxy
resin and the like are particularly preferable because the
viscosity of the component (H) is not excessively high.
[0147] As the isocyanate compound, especially preferred is an
addition reaction product obtained by mixing and reacting one
molecule of a bifunctional isocyanate having a toluene skeleton
such as tolylene diisocyanate (e.g.,
1-methylbenzene-2,4-diisocyanate, 1-methylbenzene-2,5-diisocyanate,
1-methylbenzene-2,6-diisocyanate, or
1-methylbenzene-3,5-diisocyanate) as an isocyanate compound with
two molecules of bisphenol A diglycidyl ether as an epoxy resin,
because the workability of the prepreg at normal temperature and
the heat resistance of a cured product of the epoxy resin
composition can be improved.
[0148] Examples of the commercial products of the epoxy resin
(component (H)) having an oxazolidone ring structure include
AER4152, AER4151, LSA3301, and LSA2102 (each being a product name
of Asahi Kasei E-materials Corp.); ACR1348 (product name of ADEKA
Co., Ltd.); DER 852 and DER 858 (each being a product name of THE
DOW CHEMICAL COMPANY); and TSR-400 (product name of DIC,
Incorporated), all of which are preferably used in the present
invention. Among these, AER4152 and TSR-400 are particularly
preferred.
[0149] As the component (H), two or more of the epoxy resins as
described above may be used in combination.
[0150] The amount of the component (H) is preferably 5 mass parts
by mass or more and 60 mass parts by mass or less with respect to
100 mass parts of total of all the epoxy resins contained in the
epoxy resin composition of the present invention. When the amount
of the component (H) is 5 parts by mass or more, a cured resin
product having excellent heat resistance and mechanical properties
is likely to be obtained. The amount of the component (H) is more
preferably 10 mass parts or more, still more preferably 15 mass
parts or more. On the other hand, when the amount of the component
(H) is 60 parts by mass or less, a prepreg having excellent tack
and drape can be obtained, and a cured resin product having high
fracture toughness and being free of voids can be obtained. The
amount of the component (H) is more preferably 55 parts by mass or
less, still more preferably 50 parts by mass or less. The amount of
the component (H) is more preferably in the range of 10 to 55 parts
by mass, and particularly preferably in the range of 15 to 50 parts
by mass.
[0151] In the present invention, each of the amounts (parts by
mass) of the components (A), (B), (F) and (H) can also be
understood as representing the amount in terms of % by mass
relative to the total mass of all epoxy resins contained in the
epoxy resin composition of the present invention.
<Optional Component>
[0152] The present resin composition may, if necessary, contain
various known additives as long as the effects of the present
invention are not impaired, and an antioxidant or a light
stabilizer may be added to the resin composition in order to
improve the storage stability of the composition or to prevent
discoloration and degradation of a cured product layer.
[0153] Specific examples thereof include Sumilizer BHT, Sumilizer
S, Sumilizer BP-76, Sumilizer MDP-S, Sumilizer GM, Sumilizer BBM-S,
Sumilizer WX-R, Sumilizer NW, Sumilizer BP-179, Sumilizer BP-101,
Sumilizer GA-80, Sumilizer TNP, Sumilizer TPP-R, and Sumilizer P-16
(each manufactured by Sumitomo Chemical Co., Ltd.); Adeka Stab
AO-20, Adeka Stab AO-30, Adeka Stab AO-40, Adeka Stab AO-50, Adeka
Stab AO-60, Adeka Stab AO-70, Adeka Stab AO-80, Adeka Stab AO-330,
Adeka Stab PEP-4C, Adeka Stab PEP-8, Adeka Stab PEP-24G, Adeka Stab
PEP-36, Adeka Stab HP-10, Adeka Stab 2112, Adeka Stab 260, Adeka
Stab 522A, Adeka Stab 329K, Adeka Stab 1500, Adeka Stab C, Adeka
Stab 135A, and Adeka Stab 3010 (each manufactured by Adeka
Corporation); Tinuvin 770, Tinuvin 765, Tinuvin 144, Tinuvin 622,
Tinuvin 111, Tinuvin 123, and Tinuvin 292 (each manufactured by
Ciba Specialty Chemicals); Fancryl FA-711M and FA-712HM (each
manufactured by Hitachi Chemical Company, Ltd.); and the like.
[0154] The amounts of the antioxidant and the light stabilizer are
not specifically limited, and each may range from preferably 0.001
to 5 parts by mass, more preferably 0.01 parts to 3 parts by mass,
based on the total of all epoxy resins and all (meth)acrylate
compounds contained in the curable resin composition.
[0155] Examples of other additives include known additives, such as
elastomers, thermoplastic elastomers, flame retardants (e.g.,
phosphorus-containing epoxy resins, red phosphorus, phosphazene
compounds, phosphate salts, phosphate esters, etc.), silicone oils,
wetting dispersants, antifoaming agents, defaoming agents, natural
waxes, synthetic waxes, metal salts of linear fatty acids, acid
amides, esters, mold release agents such as paraffins, crystalline
silica, fused silica, calcium silicate, alumina, calcium carbonate,
talc, powders of barium sulfate or the like, metal oxides, metal
hydroxides, glass fibers, carbon nanotubes, inorganic fillers such
as fullerenes, carbon fibers, organic fillers such as cellulose
nanofibers, inorganic fillers subjected to surface organic
treatment, etc., carbon black, coloring agents such as Bengala,
silane coupling agents, and conductive materials. Furthermore, if
necessary, a slip agent, a leveling agent, a polymerization
inhibitor such as hydroquinone monomethyl ether, an ultraviolet
light absorber and the like may also be blended.
[0156] One of these may be used alone, or two or more of these may
be used in combination.
<Viscosity of Curable Resin Composition>
[0157] The lower limit value of the viscosity of the present resin
composition at 30.degree. C. is preferably 100 Pas or more, more
preferably 300 Pas or more, and still more preferably 500 Pas or
more, from the viewpoint of adjustment of tack on the surface of
the prepreg to be obtained and workability. The upper limit value
of the viscosity is preferably 1,000,000 Pas or less, more
preferably 900,000 Pas or less, and still more preferably 800,000
Pas or less.
[0158] The viscosity of the present resin composition at 60.degree.
C. is preferably 10 Pas or more, more preferably 20 Pas or more,
and still more preferably 30 Pas or more, from the viewpoint of the
quality of the prepreg to be obtained. In addition, from the
viewpoint of impregnation into the reinforcing fiber mass and
molding processability of a prepreg, the viscosity is preferably
1,000 Pas or less, more preferably 900 Pas or less, and still more
preferably 800 Pas or less.
[0159] With respect to the minimum viscosity of the present resin
composition, the lower limit value thereof is preferably 0.05 Pas,
more preferably 0.07 Pas, and still more preferably 0.1 Pas, from
the viewpoint of flowability control of the resin during the
molding (suppression of alignment disorder of reinforcing fibers).
The upper limit value of the minimum viscosity is preferably 50
Pas, more preferably 40 Pas, and still more preferably 30 Pas.
[0160] The minimum viscosity is defined as a point at which the
viscosity is the lowest in the viscosity curve obtained when the
viscosity of the curable resin composition is measured in the
temperature rising mode.
[0161] The viscosity of the curable resin composition is
determined, for example, by a rotational viscometer (product name
"AR-G2", manufactured by TA Instruments) using 25 mm.phi. parallel
plates under the following conditions: plate gap of 500 .mu.m,
heating rate of 2.degree. C./min, angular velocity of 10 rad/sec,
and stress of 300 Pa.
<Pot Life of Curable Resin Composition>
[0162] The present resin composition is excellent in pot life. For
example, when the glass transition point of the curable resin
composition is measured immediately after compounding and after
having been stored for 90 days at a temperature 20.degree. C. under
a humidity 50%, the increase in the glass transition point after 90
days can be suppressed to 20.degree. C. or less. The suppression of
increase in the glass transition point to 20.degree. C. or less is
favorable in that, even when the curable resin composition of the
present invention is made into a prepreg and then stored for a long
time at normal temperature, the reaction of the matrix resin is
suppressed, the tack and drape of the prepreg remain within
preferable ranges, and the prepreg remain suitable for handling.
More preferably, the increase in the glass transition point is
suppressed to 15.degree. C. or less. The glass transition point can
be determined by differential scanning calorimetry (DSC).
<Physical Properties of Resin Plate>
[0163] With respect to the curable resin composition of the present
invention, the flexural modulus of the cured resin product is
preferably in the range of 3.5 to 6 GPa, and the elongation at
break of the cured resin product is preferably in the range of 7 to
15%. More preferably, the flexural modulus is 3.7 to 5 GPa and the
elongation at break is 8 to 14%. When the flexural modulus is less
than 3.5 GPa or the elongation at break is well over 15%, the
static strength of the fiber-reinforced composite material may
become insufficient. When the flexural modulus exceeds 6 GPa or the
elongation at break is less than 7%, the toughness of the
fiber-reinforced composite material is likely to become
insufficient, and the impact resistance of the fiber-reinforced
composite material may become insufficient.
<Method for Producing Curable Resin Composition and Its
Use>
[0164] As a non-limiting example of the method for producing the
curable resin composition of the present invention, the resin
composition can be produced by mixing the components described
above.
[0165] As a method for mixing the components, a method using a
mixer such as a triple roll mill, a planetary mixer, a kneader, a
homogenizer, a homodisper, etc. can be mentioned.
[0166] For example, as described later, the present resin
composition can be used to produce a prepreg by impregnating a
reinforcing fiber mass with the resin composition. In addition, a
film of the present resin composition can be obtained by applying
the present resin composition to a release paper and curing the
resin composition.
<Effects>
[0167] The present resin composition described above includes the
component (A), the component (B), the component (C) and the
component (D) which are described above, and, if necessary, the
component (H), the component (E), the component (F), the component
(G) and other additives; therefore, the use of the present resin
composition enables the production of a fiber-reinforced composite
material excellent in mechanical properties.
[Molded Article]
[0168] The molded article of the present invention is formed from
the cured product of the curable resin composition of the present
invention described above.
[0169] As a method for molding the curable resin composition, for
example, the molding can be performed by an injection molding
method (including insert molding using a film, a glass plate,
etc.), an injection compression molding method, an extrusion
molding method, a blow molding method, a vacuum molding method, an
air-pressure molding method, a calendar molding method, and an
inflation molding method. Among these, an injection molding method
and an injection compression molding method are preferable because
molded articles with excellent mass productivity and high
dimensional accuracy can be obtained, but the present invention is
not limited thereto.
[0170] Since the molded article of the present invention is formed
by molding the curable resin composition of the present invention,
the molded article is excellent in mechanical properties;
therefore, for example, the molded article is applicable to
products for vehicles, housings for mobile devices, products for
furniture, building materials and the like.
<Film Formed of Curable Resin Composition>
[0171] In one embodiment of the molded article of the present
invention, the molded article is in the form of a film. This film
is useful as an intermediate material for producing a prepreg, and
as a surface protection film or an adhesive film when cured after
being attached to a substrate.
[0172] Further, the method of such use is not limited, but it is
preferable to apply the curable resin composition of the present
invention to the surface of a substrate such as a release paper.
The obtained coating layer in an uncured state may be attached to
another substrate, followed by curing to obtain a film, or the
coating layer per se may be cured so as to be used a film.
[Prepreg]
[0173] The prepreg of the present invention is formed of a mass of
reinforcing fibers impregnated with the above-mentioned curable
resin composition of the present invention. As a method of
impregnating the reinforcing fiber mass with the present resin
composition, a known method may be used, non-limiting examples of
which include a wet method in which the present resin composition
is dissolved in a solvent such as methyl ethyl ketone or methanol
to lower the viscosity thereof and then allowed to impregnate the
reinforcing fiber mass, and a hot melt method (dry method) in which
the present resin composition is heated to lower the viscosity
thereof and then allowed to impregnate the reinforcing fiber
mass.
[0174] The wet method is a method in which reinforcing fibers are
immersed in a solution of the curable resin composition, then
pulled out of the solution, and the solvent is evaporated using an
oven or the like. On the other hand, examples of the hot melt
method include a method in which the reinforcing fibers are
directly impregnated with the curable resin composition with its
viscosity reduced by heating, and a method in which a film is
prepared by coating the curable resin composition on a release
paper or the like, which is then laminated on one of or both sides
of the reinforcing fibers, followed by heating and pressurizing to
impregnate the reinforcing fibers with the resin.
[0175] The hot melt method is preferable because substantially no
solvent remains in the prepreg.
[0176] The amount of the curable resin composition in the prepreg
of the present invention (hereinafter referred to as "resin
content") is preferably 15 to 50% by mass, more preferably 20 to
45% by mass, and still more preferably 25 to 40% by mass, based on
the total (100%) mass of the prepreg of the present invention. When
the resin content is 15% by mass or more, sufficient adhesion
strength between the reinforcing fiber mass and the curable resin
composition can be secured. When the resin content is 50% by mass
or less, high mechanical properties can be maintained.
[0177] The reinforcing fibers constituting the reinforcing fiber
mass are not particularly limited, and those known as reinforcing
fibers constituting the fiber-reinforced composite material may be
appropriately selected depending on the application and the like.
Specific example of usable reinforcing fibers include various
inorganic fibers or organic fibers such as carbon fibers, aramid
fibers, nylon fibers, high strength polyester fibers, glass fibers,
boron fibers, alumina fibers, silicon nitride fibers and the like.
Among these, carbon fibers, aramid fibers, glass fibers, boron
fibers, alumina fibers and silicon nitride fibers are preferable
from the viewpoint of specific strength and specific elasticity,
and carbon fibers are particularly preferable from the viewpoint of
mechanical properties and weight reduction. When carbon fibers are
used as the reinforcement fibers, the carbon fibers may be
surface-treated with a metal.
[0178] One kind of these reinforcing fibers may be used alone, or
two or more kinds thereof may be used in combination.
[0179] From the viewpoint of the rigidity of the fiber-reinforced
composite material obtained by curing the prepreg of the present
invention, the strand tensile strength of the carbon fibers is
preferably 1 to 9 GPa, more preferably 1.5 to 9 GPa, and the strand
tensile modulus of the carbon fibers is preferably 150 to 1,000
GPa, more preferably 200 to 1,000 GPa.
[0180] The strand tensile strength and strand tensile modulus of
the carbon fibers are values measured according to J1S R 7601:
1986.
[0181] The form of the reinforcing fiber mass is not particularly
limited, and the reinforcing fiber mass may be in any form adopted
by a base material used in conventional prepreg. For example, the
reinforcing fiber mass may be one in which reinforcing fibers are
oriented in one direction (UD: Unidirection), woven or non-woven
fibers, or a non-crimp fabric.
[0182] Since the prepreg of the present invention is formed by
impregnating the reinforcing fiber mass with the epoxy resin
composition of the present invention, the prepreg can be used as a
raw material of fiber-reinforced plastic excellent in mechanical
properties.
[Fiber-Reinforced Plastic]
[0183] The fiber-reinforced plastic of the present invention
includes a cured product of the above-mentioned curable resin
composition of the present invention and reinforcing fibers.
[0184] As a non-limiting example of the method for producing the
fiber-reinforced plastic of the present invention, for example, the
fiber-reinforced plastic can be obtained by laminating layers of
the above-mentioned prepreg of the present invention, followed by
molding the resulting laminate, for example, by heat-curing the
curable resin while applying pressure to the laminate.
[0185] The fiber-reinforced plastic of the present invention
preferably contains carbon fibers as the reinforcing fibers because
the resulting fiber-reinforced plastic is excellent in mechanical
properties, flame retardancy, heat resistance, electromagnetic wave
shielding ability and the like.
[0186] Non-limiting examples of the molding method for producing
the fiber-reinforced plastic of the present invention includes a
press molding method, an autoclave molding method, a bag molding
method, a wrapping tape method, an internal pressure molding
method, a sheet wrap molding method, and a method in which a
filament or preform of a reinforcing fiber is impregnated with the
curable resin composition, followed by curing to produce a molded
article, e.g., RTM (Resin Transfer Molding), VaRTM (Vacuum assisted
Resin Transfer Molding: vacuum resin impregnation manufacturing
method), filament winding, and RFI (Resin Film Infusion).
[0187] The wrapping tape method is a method for forming a tubular
body made of the fiber-reinforced composite material by winding the
prepreg around a core such as a mandrel, and is suitable for
producing a rod-like body such as a golf shaft or a fishing rod.
More specifically, a prepreg is wound around a mandrel, and a
wrapping tape formed of a thermoplastic resin film is wound around
the prepreg for fixing and pressurizing the prepreg. Then, the
epoxy resin composition is heated and cured in an oven, and
subsequently the core is removed to obtain a fiber-reinforced
plastic tube.
[0188] Further, in the internal pressure molding method, a preform
obtained by winding a prepreg around an inner pressure-applying
body such as a thermoplastic resin tube is set in a mold, and
subsequently a high pressure gas is introduced into the inner
pressure-applying body for applying a pressure, while heating the
mold at the same time, to thereby perform molding. The inner
pressure molding method can be especially preferably used in the
case where a product having a complicated shape such as a golf
shaft, a baseball bat or a racket for tennis or badminton is
produced by molding.
[0189] A fiber-reinforced plastic using a cured product of the
curable resin composition of the present invention as a matrix
resin is suitably used in sports applications, general industrial
applications, and aerospace applications. More specifically, in
sport applications, the fiber-reinforced plastic is suitably used
for golf shafts, fishing rods, tennis and badminton rackets, sticks
for hockey etc., and ski poles. Furthermore, in general industrial
applications, the fiber-reinforced plastic is suitably used for
structural materials of moving bodies such as automobiles, ships,
and railway vehicles, drive shafts, leaf springs, wind turbine
blades, pressure vessels, flywheels, paper rollers, roofing
materials, cables, repair reinforcement materials, and the
like.
<Structured Body>
[0190] A structured body can be obtained from the fiber-reinforced
plastic of the present invention described above. This structured
body may consist only of the fiber-reinforced plastic of the
present invention, or is composed of the fiber-reinforced plastic
of the present invention and other materials (for example, metals,
injection molded thermoplastic resin member, etc.).
[0191] This structured body is partially or entirely composed of
the fiber-reinforced plastic of the present invention, whereby the
structured body excels in flame retardancy and heat resistance.
[0192] This structured body is also applicable to, for example,
interior parts of aircrafts and automobiles, and housings for
electric and electronic devices.
[Fiber-Reinforced Plastic Tube]
[0193] The fiber-reinforced plastic tube is a fiber-reinforced
plastic of the present invention which is tubular. That is, the
fiber-reinforced plastic tube is a tubular fiber-reinforced plastic
obtained by laminating, curing and molding the above-mentioned
prepregs of the present invention by a known molding method such as
a wrapping tape method.
[0194] Since the fiber-reinforced plastic tube of the present
invention has excellent fracture strength and elastic modulus, it
can be suitably used for golf shafts, fishing rods and the
like.
[0195] The fiber-reinforced plastic tube can be obtained from a
unidirectional prepreg in which reinforcing fibers aligned in one
direction are impregnated with the resin composition of the present
invention. The shape of the tube is not limited, but, for example,
a composite material tube may be produced by laminating 2 plys of
prepregs so that the fiber directions of the unidirectional
prepregs are -45.degree. and +45.degree. with respect to the
cylindrical axis direction, and further laminating 1 ply of prepreg
so that the fiber direction of the unidirectional prepreg is
parallel to the cylindrical axial direction, and the obtained
composite material tube may be evaluated. The mandrel used here is
a stainless steel round bar.
[0196] Specifically, as a non-limiting example of method for
producing the fiber-reinforced plastic tube, the tube can be
produced by the method described in the following (I) to (V).
[0197] (I) Two sheets of prepreg, each having a size of 200 mm in
length.times.72 mm in width, are cut out from the prepared
unidirectional prepreg such that the fiber axis direction is
45.degree. relative to the long side direction. The two sheets of
prepreg are laminated such that the fiber directions of the two
sheets intersect each other and one side of each sheet protrudes by
9 mm in the short side direction. [0198] (II) The laminated
prepregs obtained above are wound around a release-treated mandrel
so that the long side of the laminated prepregs and the axis of the
mandrel are aligned in the same direction. [0199] (III) A
rectangular prepreg having a length of 200 mm and a width of 153 mm
is cut out from the prepared unidirectional prepreg and wound
around a mandrel such that the long side direction of the prepreg
is aligned with the fiber direction of the prepreg, and the fiber
direction is aligned with the mandrel axial direction. [0200] (IV)
The resulting is covered by wrapping thereon a heat resistant film
tape as a wrapping tape, and is thermoformed in a curing furnace at
130.degree. C. for 90 minutes. The width of the wrapping tape is 15
mm, the tension is 3 N, and the winding pitch (displacement
distance in winding) is 1 mm, and this wrapping tape is wrapped so
as to have the same thickness as the laminate. [0201] (V)
Thereafter, the mandrel is removed and the wrapping tape is removed
to obtain a fiber-reinforced plastic tube.
EXAMPLES
[0202] Hereinbelow, the present invention will be specifically
described by way of Examples which should not be construed as
limiting the present invention. The raw materials used in the
Example and Comparative Examples are shown below.
[0203] The softening point and the epoxy equivalent were measured
under the following conditions.
[0204] 1) Softening point: measured in accordance with JIS-K7234:
2008 (ring and ball method).
[0205] 2) Epoxy equivalent: measured in accordance with JIS-K 7236:
2001.
"Raw Materials"
<Component (A)>
[0206] jER 1007: Solid bisphenol A epoxy resin (softening point
128.degree. C., manufactured by Mitsubishi Chemical Corporation,
product name "jER 1007").
[0207] jER4007P: Solid bisphenol F epoxy resin (softening point:
108.degree. C., manufactured by Mitsubishi Chemical Corporation,
product name: "jER4007P").
[0208] jER4004P: Solid bisphenol F epoxy resin (softening point
85.degree. C., manufactured by Mitsubishi Chemical Corporation,
product name "jER4004P").
<Component (B)>
[0209] jER 828: Liquid bisphenol A epoxy resin (epoxy equivalent
189 g/eq, manufactured by Mitsubishi Chemical Corporation, product
name "jER 828").
[0210] jER 807: Liquid bisphenol F epoxy resin (epoxy equivalent
170 g/eq, manufactured by Mitsubishi Chemical Corporation, product
name "jER 807").
<Component (C)>
[0211] Neopentyl glycol diacrylate
[0212] Polyethylene glycol #200 dimethacrylate
[0213] Trimethylolpropane trimethacrylate
[0214] Pentaerythritol tetraacrylate
[0215] Dipentaerythritol hexaacrylate
[0216] Dioxane glycol diacrylate
[0217] Isocyanuric acid EO-modified di- and tri-acrylates
[0218]
2-[5-ethyl-5-[(acryloyloxy)methyl]-1,3-dioxane-2-yl]-2,2-dimethylet-
hyl acrylate
[0219] Dimethylol-tricyclodecane diacrylate
[0220] Pentaerythritol triacrylate toluene diisocyanate urethane
prepolymer
[0221] Pentaerythritol triacrylate hexamethylene diisocyanate
urethane prepolymer
<Component (d1)>
[0222] DICY15: dicyandiamide (active hydrogen equivalent 21 g/eq,
manufactured by Mitsubishi Chemical Corporation, product name "jER
Cure D1CY15").
[0223] 1400F: dicyandiamide (active hydrogen equivalent 21 g/eq,
manufactured by Air Products and Chemicals, Inc., product name
"DICYANEX 1400F").
[0224] DCMU-99: 3-(3,4-dichlorophenyl)-1,1-dimethylurea (Hodogaya
Chemical Co.,Ltd., trade name "DCMU-99").
[0225] Omicure 94: N,N-dimethyl-N'-phenylurea (manufactured by PTI
Japan, Ltd., product name "Omicure 94").
[0226] U-CAT 3513N: isophorone diamine dimethyl urea (manufactured
by San-Apro Ltd., product name "U-CAT 3513N").
[0227] Omicure 24: 2,4-bis(3,3-dimethylureido) toluene
(manufactured by PTI Japan, Ltd., product name "Omicure 24").
<Component (d2)>
[0228] Di-t-hexyl peroxide (10-hour half-life temperature
116.4.degree. C.).
[0229] Dicumyl peroxide (10-hour half-life temperature 116.
.degree. C.).
<Component (E)>
[0230] VINYLEC E: polyvinyl formal resin (manufactured by JNC
Corporation, product name "VINYLEC E").
<Component (H)>
[0231] TSR-400: oxazolidone ring-containing epoxy resin (epoxy
equivalent 338 g/eq, manufactured by DIC Corporation, product name
"TSR-400").
[0232] LSA 3301: oxazolidone ring-containing epoxy resin (epoxy
equivalent 403 g/eq, manufactured by Asahi Kasei Corporation,
product name "LSA 3301").
<Carbon Fiber>
[0233] TR: manufactured by Mitsubishi Chemical Corporation, product
name "PYROFIL TR50S15L".
[0234] MR: manufactured by Mitsubishi Chemical Corporation, product
name "PYROFIL MR70 12P".
Example 1
[0235] Using jER4007P as the component (A), jER807 as the component
(B), neopentyl glycol diacrylate as the component (C), DICY15 and
DCMU-99 as the component (d1), di-t-hexyl peroxide as the component
(d2), a curable resin composition was prepared as follows.
[0236] First, according to the compositional ratio described in
Table 1, the component (B) (liquid) and the component (d1) (solid)
were weighed into a container such that the mass ratio of solid
component to liquid component became 1:1, followed by addition of a
masterbatch containing the component (D). The resulting was stirred
to mix the components. The resulting was further finely mixed with
a three-roll mill to obtain a curing agent-containing
masterbatch.
[0237] Subsequently, from the components described in Table 1, the
component (A) and the component (B) other than used in the curing
agent-containing masterbatch were weighed into a flask, heated to
140.degree. C. using an oil bath, and allowed to be dissolved and
mixed. After cooling to about 65.degree. C., the component (C), the
curing agent-containing master batch, and the component (d2) were
added and stirred to obtain an uncured curable resin
composition.
"Production of Resin Plate"
[0238] The uncured curable resin composition was poured between two
glass plates, molded into a plate, heated at 2.degree. C./min,
heat-cured at an oven atmosphere temperature of 135.degree. C. for
90 minutes, to produce a 2 mm-thick resin plate.
"Production of Prepreg"
[0239] The uncured curable resin composition was formed into a film
by a comma coater ("M-500", manufactured by Hirano Tecseed Co.,
Ltd.), and a resin film with a resin coating weight of 16.7
g/m.sup.2 was produced. Thus produced resin films were laminated on
both sides of a carbon fiber sheet with a basis weight of 100
g/m.sup.2 obtained by aligning carbon fibers, and the resulting was
fed into heating rolls to allow the carbon fiber sheet to be
impregnated with the resin, so as to obtain an uncured
unidirectional prepreg having a basis weight of 133.4 g/m.sup.2 and
a resin content of 25% by mass.
"Production of Fiber-Reinforced Plastic Plate"
[0240] The uncured prepreg with a resin content of 25% by mass
obtained above was cut into sheets of 300 mm.times.300 mm, and 24
sheets were laminated such that the relation between the angles of
fiber directions of the sheets was
[0.degree./0.degree./0.degree./0.degree./0.degree./0.degree./0.degree./0.-
degree./0.degree./0.degree./0.degree./0.degree./0.degree./0.degree./0.degr-
ee./0.degree./0.degree./0.degree./0.degree./0.degree./0.degree./0.degree./-
0.degree./0.degree./0.degree./0.degree.], thereby obtaining a
laminate. The laminate was heated in an autoclave at 2.degree.
C./min under a pressure of 0.04 MPa, held at 80.degree. C. for 60
minutes, then heated at 2.degree. C./min under a pressure of 0.6
MPa, and held at 130.degree. C. for 90 minutes, thereby heat-curing
the resin to obtain a fiber-reinforced plastic plate having a
thickness of 2.1 mm.
"Fabrication of Fiber-Reinforced Plastic Tube"
[0241] The fiber-reinforced plastic tube was produced by the method
described in (I) to (VI) below. [0242] (I) Two sheets of
rectangular prepreg, each having a size of 200 mm in
length.times.72 mm in width, were cut out from the unidirectional
prepreg with a resin content of 25% by mass prepared above such
that the fiber axis direction was 45.degree. relative to the long
side direction. The two sheets pf prepreg were laminated such that
the fiber directions of the two sheets intersect each other and one
side of each sheet protrudes by 9 mm in the short side direction.
[0243] (II) The laminated prepregs obtained above were wound around
a release-treated mandrel so that the long side of the laminated
prepregs and the axis of the mandrel were aligned in the same
direction. The mandrel used was a stainless steel round rod having
a diameter of 6 mm and a length of 300 mm. [0244] (III) A
rectangular prepreg having a length of 200 mm and a width of 153 mm
was cut out from the produced unidirectional prepreg and wound
around a mandrel such that the long side direction of the prepreg
was aligned with the fiber direction of the prepreg, and the fiber
direction was aligned with the mandrel axial direction. [0245] (IV)
The resulting was covered by wrapping thereon a heat resistant film
tape as a wrapping tape, and was thermoformed in a curing furnace
at 130.degree. C. for 90 minutes. The width of the wrapping tape
was 15 mm, the tension was 3 N, and the winding pitch (displacement
distance in winding) was 1 mm, and this wrapping tape was wrapped
so as to have the same thickness as the laminate. [0246] (V)
Thereafter, the mandrel was removed and the wrapping tape was
removed to obtain a fiber-reinforced plastic tube having an inner
diameter of 6 mm and a length of 200 mm.
[0247] With respect to the produced resin plate, prepreg and
fiber-reinforced plastic, various measurements and evaluations were
performed according to the measurement and evaluation methods
described below. The results are shown in Table 1.
"Measurement of Flexural Strength, Flexural Modulus, Elongation at
Break (Fracture Strain) of Resin Plate"
[0248] The resin plate having a thickness of 2 mm obtained in the
section "Production of Resin Plate" was processed into a test piece
of 60 mm in length.times.8 mm in width. With respect to the test
piece, the flexural strength, flexural modulus and elongation at
break (fracture strain) of the resin plate were measured using a
universal tester ("INSTRON 5565", manufactured by INSTRON) equipped
with a 3-point bending jig (indenter R=3.2 mm, support R=3.2 mm,
distance between supports (L)=32 mm) at a temperature of 23.degree.
C. under a humidity of 50% RH with a crosshead speed of 2
mm/min.
"Measurement of 0.degree. Flexural Strength/Flexural Modulus, and
90.degree. Flexural Strength/Flexural Modulus of Fiber-Reinforced
Plastic Plate"
[0249] The fiber-reinforced plastic plate having a thickness of 2.1
mm produced in the section "Preparation of Fiber-Reinforced Plastic
Plate" was processed into a test piece of 60 mm in
length.times.12.7 mm in width. With respect to the test piece, the
flexural properties of the fiber-reinforced plastic plate in terms
of 0.degree. flexural strength/flexural modulus, and 90.degree.
flexural strength/flexural modulus were measured using a universal
tester ("INSTRON 5565", manufactured by INSTRON) equipped with a
3-point bending jig (indenter R=5.0 mm, support R=3.2 mm) with
L/d=16 (Lis a distance between supports and d is a thickness of the
test piece) and a crosshead speed (per minute) of
(L2.times.0.01)/(6.times.d).
"Measurement of Flexural Strength, Flexural Modulus and Strain at
Maximum Load of Fiber-Reinforced Plastic Tube"
[0250] With respect to the fiber-reinforced plastic tube having an
inner diameter of 6 mm and a length of 200 mm, which was obtained
in the section "Fabrication of Fiber-Reinforced Plastic Tube", the
flexural properties of the fiber-reinforced plastic tube in terms
of flexural strength, flexural modulus and strain at maximum load
were measured using a universal tester ("INSTRON 5565",
manufactured by INSTRON) equipped with a 3-point bending jig
(indenter R=75 mm, support R=12.5 mm, distance between supports
(L)=150 mm) with a crosshead speed of 20 mm/min.
Examples 2 to 24, Comparative Example 1
[0251] Curable resin compositions were prepared in the same manner
as in Example 1 except that the compositional ratios were changed
to those shown in Tables 1 and 2, and resin plates, prepregs,
fiber-reinforced plastic plates, fiber-reinforced plastic tubes
were produced, on which various measurements and evaluations were
performed. The evaluation results are shown in Table 1 and Table 2.
(In Tables 1 and 2, each of the amounts of the component (A) and
the component (B) is an amount (parts by mass) with respect to 100
parts by mass of total of all epoxy resins, the amount of the
component (d2) is an amount (part by mass) with respect to 100
parts by mass of total of all epoxy resins and all (meth)acrylate
compounds contained in the curable resin composition, and the
amount of other components is an amount (part by mass) with respect
to 100 parts by mass of total of all epoxy resins.)
TABLE-US-00001 TABLE 1 Example Composition (part by mass) 1 2 3 4 5
6 7 Component (A) jER1007 0 0 0 0 50 0 0 jER4007P 50 50 50 50 0 50
50 Component (B) jER828 0 0 0 0 50 0 0 jER807 50 50 50 50 0 50 50
Component (C) Neopentyl glycol diacrylate 25 0 0 0 0 0 0
Polyethylene glycol # 200 dimethacrylate 0 25 0 0 0 0 0
Trimethylolpropane triacrylate 0 0 0 0 0 0 0 Trimethylolpropane
trimethacrylate 0 0 25 0 0 0 0 Pentaerythritol tetraacrylate 0 25 0
25 25 0 0 Dipentaerythritol hexaacrylate 0 0 0 0 0 25 5 Isocyanuric
acid EO-modified di- and tri-acrylates 0 0 0 0 0 0 0
2[5-ethyl-5-[(acryloyloxy)methyl]-1,3-dioxane-2-yl]- 0 0 0 0 0 0 0
2,2-dimethylethyl acrylate Dimethylol-tricyclodecane diacrylate 0 0
0 0 0 0 0 Pentaerythritol triacrylate toluene diisocyanate 0 0 0 0
0 0 0 urethane prepolymer Pentaerythritol triacrylate hexamethylene
0 0 0 0 0 0 0 diisocyanate urethane prepolymer Component (D) (d1)
DICY15 4.4 4.4 4.4 4.4 4 4.4 4.4 1400F 0 0 0 0 0 0 0 DCMU-99 3 3 3
3 3 3 3 Omicure94 0 0 0 0 0 0 0 (d2) Di-t-hexyl peroxide 0.6 0.5
0.7 0.8 0.8 0.8 0.2 Component (E) VINYLEC E 0 0 0 0 0 0 0 Physical
Properties of Resin Plate Flexural Strength [MPa] 177 164 182 179
170 174 166 Flexural Modulus [GPa] 3.95 3.79 4.09 4.11 3.8 3.96
3.73 Elongation at Break [%] 12.8 13.9 7.4 10.2 11.4 10.1 13.7
Example Composition (part by mass) 8 9 10 11 12 13 Component (A)
jER1007 0 0 0 0 0 0 jER4007P 50 50 50 50 50 50 Component (B) jER828
0 0 0 0 0 0 jER807 50 50 50 50 50 50 Component (C) Neopentyl glycol
diacrylate 0 0 0 0 0 0 Polyethylene glycol # 200 dimethacrylate 0 0
0 0 0 0 Trimethylolpropane triacrylate 0 0 0 0 0 0
Trimethylolpropane trimethacrylate 0 0 0 0 0 0 Pentaerythritol
tetraacrylate 0 0 0 0 0 0 Dipentaerythritol hexaacrylate 5 15 15 35
35 45 Isocyanuric acid EO-modified di- and tri-acrylates 0 0 0 0 0
0 2[5-ethyl-5-[(acryloyloxy)methyl]-1,3-dioxane-2-yl]- 0 0 0 0 0 0
2,2-dimethylethyl acrylate Dimethylol-tricyclodecane diacrylate 0 0
0 0 0 0 Pentaerythritol triacrylate toluene diisocyanate 0 0 0 0 0
0 urethane prepolymer Pentaerythritol triacrylate hexamethylene 0 0
0 0 0 0 diisocyanate urethane prepolymer Component (D) (d1) DICY15
4.4 4.4 4.4 4.4 4.4 4.4 1400F 0 0 0 0 0 0 DCMU-99 3 3 3 3 3 3
Omicure94 0 0 0 0 0 0 (d2) Di-t-hexyl peroxide 0.7 0.5 0.8 0.9 1.1
1.0 Component (E) VINYLEC E 0 0 0 0 0 0 Physical Properties of
Resin Plate Flexural Strength [MPa] 165 171 167 177 177 176
Flexural Modulus [GPa] 4.07 3.84 3.83 4.39 3.96 4.29 Elongation at
Break [%] 14.1 13.5 10.9 7.7 11.9 8.4
TABLE-US-00002 TABLE 2 Example Composition (part by mass) 14 15 16
17 18 19 20 Component (A) jER1007 0 0 0 0 0 0 50 jER4007P 50 50 50
50 50 50 0 Component (B) jER828 0 0 0 0 0 0 50 jER807 50 50 50 50
50 50 0 Component (C) Neopentyl glycol diacrylate 0 0 0 0 0 0 0
Polyethylene glycol # 200 dimethacrylate 0 0 0 0 0 0 0
Trimethylolpropane triacrylate 0 0 0 0 0 0 0 Trimethylolpropane
trimethacrylate 0 0 0 0 0 0 0 Pentaerythritol tetraacrylate 0 0 0 0
0 0 0 Dipentaerythritol hexaacrylate 40 25 25 25 25 25 0
Isocyanuric acid EO-modified di- and tri-acrylates 0 0 0 0 0 0 25
2[5-ethyl-5-[(acryloyloxy)methyl]-1,3-dioxane-2-yl]- 0 0 0 0 0 0 0
2,2-dimethylethyl acrylate Dimethylol-tricyclodecane diacrylate 0 0
0 0 0 0 0 Pentaerythritol triacrylate toluene diisocyanate 0 0 0 0
0 0 0 urethane prepolymer Pentaerythritol triacrylate hexamethylene
0 0 0 0 0 0 0 diisocyanate urethane prepolymer Component (D) (d1)
DICY15 4.4 0 0 4.4 4.4 0 4.4 1400F 0 4.4 3.8 0 0 4.4 0 DCMU-99 3 3
3 3 3 0 3 Omicure94 0 0 0 0 0 2 0 (d2) Di-t-hexyl peroxide 1.4 0.8
0.8 0.8 0.8 0.8 0.8 Component (E) VINYLEC E 0 0 0 3 5 0 0 Physical
Properties of Resin Plate Flexural Strength [MPa] 174 180 179 172
169 170 178 Flexural Modulus [GPa] 3.80 4.23 4.17 4.12 4.02 3.81
4.07 Elongation at Break [%] 9.1 10.2 9.2 10.8 11.98 13.0 12.5
Comparative Example Example Composition (part by mass) 21 22 23 24
1 Component (A) jER1007 0 0 0 0 50 jER4007P 50 50 50 50 0 Component
(B) jER828 0 0 0 0 50 jER807 50 50 50 50 0 Component (C) Neopentyl
glycol diacrylate 0 0 0 0 0 Polyethylene glycol # 200
dimethacrylate 0 0 0 0 0 Trimethylolpropane triacrylate 0 0 0 0 0
Trimethylolpropane trimethacrylate 0 0 0 0 0 Pentaerythritol
tetraacrylate 0 0 0 0 0 Dipentaerythritol hexaacrylate 0 0 0 0 0
Isocyanuric acid EO-modified di- and tri-acrylates 0 0 0 0 0
2[5-ethyl-5-[(acryloyloxy)methyl]-1,3-dioxane-2-yl]- 25 0 0 0 0
2,2-dimethylethyl acrylate Dimethylol-tricyclodecane diacrylate 0
25 0 0 0 Pentaerythritol triacrylate toluene diisocyanate 0 0 25 0
0 urethane prepolymer Pentaerythritol triacrylate hexamethylene 0 0
0 25 0 diisocyanate urethane prepolymer Component (D) (d1) DICY15
4.4 4.4 4.4 4.4 4 1400F 0 0 0 0 0 DCMU-99 3 3 3 3 3 Omicure94 0 0 0
0 0 (d2) Di-t-hexyl peroxide 0.8 0.8 0.8 0.8 0 Component (E)
VINYLEC E 0 0 0 0 0 Physical Properties of Resin Plate Flexural
Strength [MPa] 169 166 173 173 142 Flexural Modulus [GPa] 4.0 3.94
4.02 3.96 3.15 Elongation at Break [%] 12.6 13.9 10.6 9.7 10.3
[0252] As shown in Tables 1 and 2, each of the Example was superior
to Comparative Example 1 without the component (C) in that the
resin plate was excellent in strength and elastic modulus, while
maintaining toughness. Moreover, the physical properties of the
fiber-reinforced plastic plate and the fiber-reinforced plastic
tube were improved in each of the Examples as compared to
Comparative Example 1 without the component (C).
Example 25
[0253] Using jER4007P as the component (A), jER807 as the component
(B), neopentyl glycol diacrylate as the component (C), D1CY15 and
DCMU-99 as the component (d1), di-t-hexyl peroxide as the component
(d2), and TSR-400 as the component (E), a curable resin composition
was prepared as follows.
[0254] First, according to the compositional ratio described in
Table 1, the component (B) (liquid) and the component (d1) (solid)
were weighed into a container such that the mass ratio of solid
component to liquid component became 1:1, followed by addition of a
masterbatch containing the component (D). The resulting was stirred
to mix the components. The resulting was further finely mixed with
a three-roll mill to obtain a curing agent-containing
masterbatch.
[0255] Subsequently, from the components described in Table 1, the
component (A), the component (B) other than used in the curing
agent-containing masterbatch and the component (H) were weighed
into a flask, heated to 140.degree. C. using an oil bath, and
allowed to be dissolved and mixed. After cooling to about
65.degree. C., the component (C), the curing agent-containing
master batch, and the component (d2) were added and stirred to
obtain an uncured curable resin composition.
[0256] The various measurements and evaluations were performed with
respect to the resin plate, prepreg and fiber-reinforced plastic
produced using the obtained uncured curable resin composition. The
results are shown in Table 3.
Examples 26 to 52, Comparative Examples 2 and 3
[0257] Curable resin compositions were prepared in the same manner
as in Example 25 except that the compositional ratios were changed
to those shown in Tables 1 and 2, and resin plates, prepregs,
fiber-reinforced plastic plates, fiber-reinforced plastic tubes
were produced, on which various measurements and evaluations were
performed. The evaluation results are shown in Table 3 and Table 4.
(In Tables 3 and 4, each of the amounts of the component (A), the
component (B) and the component (H) is an amount (parts by mass)
with respect to 100 parts by mass of total of all epoxy resins, the
amount of the component (d2) is an amount (part by mass) with
respect to 100 parts by mass of total of all epoxy resins and all
(meth)acrylate compounds contained in the curable resin
composition, and the amount of other components is an amount (part
by mass) with respect to 100 parts by mass of total of all epoxy
resins.)
TABLE-US-00003 TABLE 3 Example Composition (part by mass) 25 26 27
28 29 30 31 32 Component (A) jER4007P 20 20 20 20 20 20 20 20
Component (B) jER807 50 50 50 50 50 50 50 50 Component (H) TSR-400
30 30 30 30 30 30 30 30 LSA3301 0 0 0 0 0 0 0 0 Component (C)
Neopentyl glycol diacrylate 25 0 0 0 0 0 0 0 Trimethylolpropane
triacrylate 0 25 0 0 0 0 0 0 Pentaerythritol tetraacrylate 0 0 25 0
0 0 0 0 Dipentaerythritol hexaacrylate 0 0 0 25 0 0 0 0 Dioxane
glycol diacrylate 0 0 0 0 25 0 0 0 Dimethylol-tricyclodecane
diacrylate 0 0 0 0 0 25 0 0 Pentaerythritol triacrylate toluene 0 0
0 0 0 0 25 0 diisocyanate urethane prepolymer Pentaerythritol
triacrylate hexamethylene 0 0 0 0 0 0 0 25 diisocyanate urethane
prepolymer Component (D) (d1) 1400F 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4
DCMU-99 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7 Omicure94 0 0 0 0 0 0 0 0
U-CAT 3513N 0 0 0 0 0 0 0 0 (d2) Di-t-hexyl peroxide 0.8 0.8 0.8
0.8 0.8 0.8 0.8 0.8 Component (E) VINYLEC E 0 0 0 0 0 0 0 0
Flexural Properties of Flexural Strength [MPa] 174 171 182 187 175
179 184 182 Resin Plate Flexural Modulus [GPa] 3.8 3.7 3.9 4.0 3.9
4.0 4.0 3.9 Elongation at Break [%] 9 9 9 11 12 11 8 8 Fiber- TR
Strength [MPa] -- -- -- -- -- -- -- -- Reinforced Flexural Modulus
[GPa] -- -- -- -- -- -- -- -- Plastic Tube Fracture Strain [%] --
-- -- -- -- -- -- -- MR Strength [MPa] -- -- -- -- -- -- -- --
Flexural Modulus [GPa] -- -- -- -- -- -- -- -- Fracture Strain [%]
-- -- -- -- -- -- -- -- Example Composition (part by mass) 33 34 35
36 37 38 39 Component (A) jER4007P 20 20 30 50 50 50 20 Component
(B) jER807 50 50 60 40 40 40 60 Component (H) TSR-400 30 30 10 10
10 10 20 LSA3301 0 0 0 0 0 0 0 Component (C) Neopentyl glycol
diacrylate 0 0 0 0 0 0 0 Trimethylolpropane triacrylate 0 0 0 0 0 0
0 Pentaerythritol tetraacrylate 0 0 0 0 0 0 0 Dipentaerythritol
hexaacrylate 25 25 25 25 25 25 25 Dioxane glycol diacrylate 0 0 0 0
0 0 0 Dimethylol-tricyclodecane diacrylate 0 0 0 0 0 0 0
Pentaerythritol triacrylate toluene 0 0 0 0 0 0 0 diisocyanate
urethane prepolymer Pentaerythritol triacrylate hexamethylene 0 0 0
0 0 0 0 diisocyanate urethane prepolymer Component (D) (d1) 1400F
5.4 5.4 5.5 4 4 4 5.8 DCMU-99 0 0 3.7 2.7 2.7 2.7 3.9 Omicure94 2.6
0 0 0 0 0 0 U-CAT 3513N 0 2.4 0 0 0 0 0 (d2) Di-t-hexyl peroxide
0.8 0.8 0.8 0.4 0.8 2 0.8 Component (E) VINYLEC E 0 0 0 0 0 0 0
Flexural Properties of Flexural Strength [MPa] 190 185 186 172 180
177 187 Resin Plate Flexural Modulus [GPa] 4.0 3.9 4.2 4.0 4.1 4.1
4.1 Elongation at Break [%] 8 9 9 9 9 8 8 Fiber- TR Strength [MPa]
-- -- -- -- 1835 -- -- Reinforced Flexural Modulus [GPa] -- -- --
-- 68 -- -- Plastic Tube Fracture Strain [%] -- -- -- -- 11 -- --
MR Strength [MPa] -- -- -- -- 2063 -- -- Flexural Modulus [GPa] --
-- -- -- 90 -- -- Fracture Strain [%] -- -- -- -- 9 -- --
TABLE-US-00004 TABLE 4 Example Composition (part by mass) 40 41 42
43 44 45 46 47 Component (A) jER4007P 40 30 10 30 30 30 30 30
Component (B) jER807 40 40 60 40 40 40 40 40 Component (H) TSR-400
20 30 30 30 30 30 30 0 LSA3301 0 0 0 0 0 0 0 30 Component (C)
Neopentyl glycol diacrylate 0 0 0 0 0 0 0 0 Trimethylolpropane
triacrylate 0 0 0 0 0 0 0 0 Pentaerythritol tetraacrylate 0 0 0 0 0
0 0 0 Dipentaerythritol hexaacrylate 25 25 25 25 25 25 25 25
Dioxane glycol diacrylate 0 0 0 0 0 0 0 0 Dimethylol-tricyclodecane
diacrylate 0 0 0 0 0 0 0 0 Pentaerythritol triacrylate toluene 0 0
0 0 0 0 0 0 diisocyanate urethane prepolymer Pentaerythritol
triacrylate hexamethylene 0 0 0 0 0 0 0 0 diisocyanate urethane
prepolymer Component (D) (d1) 1400F 4.3 4.7 6.2 4.7 4.7 4.7 4.7 4.5
DCMU-99 2.9 3.2 4.2 3.2 3.2 3.2 3.2 2.9 Omicure94 0 0 0 0 0 0 0 0
U-CAT 3513N 0 0 0 0 0 0 0 0 (d2) Di-t-hexyl peroxide 0.8 0.4 0.8 2
0.8 0.8 0.8 0.8 Component (E) VINYLEC E 0 0 0 0 0 1 3 1 Flexural
Properties of Flexural Strength [MPa] 179 176 186 181 186 180 179
182 Resin Plate Flexural Modulus [GPa] 4.0 3.9 3.9 4.0 4.0 3.9 3.9
4.0 Elongation at Break [%] 10 8 9 8 12 8 9 8 Fiber- TR Strength
[MPa] -- -- -- -- 2051 -- -- -- Reinforced Flexural Modulus [GPa]
-- -- -- -- 71 -- -- -- Plastic Tube Fracture Strain [%] -- -- --
-- 11 -- -- -- MR Strength [MPa] -- -- -- -- 2081 -- -- -- Flexural
Modulus [GPa] -- -- -- -- 91 -- -- -- Fracture Strain [%] -- -- --
-- 9 -- -- -- Comp. Example Ex. Composition (part by mass) 48 49 50
51 52 2 3 Component (A) jER4007P 40 10 30 10 30 50 30 Component (B)
jER807 30 50 30 40 20 40 40 Component (H) TSR-400 30 40 40 50 50 10
30 LSA3301 0 0 0 0 0 0 0 Component (C) Neopentyl glycol diacrylate
0 0 0 0 0 0 0 Trimethylolpropane triacrylate 0 0 0 0 0 0 0
Pentaerythritol tetraacrylate 0 0 0 0 0 0 0 Dipentaerythritol
hexaacrylate 25 25 25 25 25 0 0 Dioxane glycol diacrylate 0 0 0 0 0
0 0 Dimethylol-tricyclodecane diacrylate 0 0 0 0 0 0 0
Pentaerythritol triacrylate toluene 0 0 0 0 0 0 0 diisocyanate
urethane prepolymer Pentaerythritol triacrylate hexamethylene 0 0 0
0 0 0 0 diisocyanate urethane prepolymer Component (D) (d1) 1400F
3.9 5.8 4.3 5.4 3.9 4 4.7 DCMU-99 2.7 3.9 2.9 3.6 2.6 2.7 3.2
Omicure94 0 0 0 0 0 0 0 U-CAT 3513N 0 0 0 0 0 0 0 (d2) Di-t-hexyl
peroxide 0.8 0.8 0.8 0.8 0.8 0 0 Component (E) VINYLEC E 0 0 0 0 0
0 0 Flexural Properties of Flexural Strength [MPa] 178 185 180 182
181 155 160 Resin Plate Flexural Modulus [GPa] 4.1 4.1 3.9 3.9 3.9
3.8 3.8 Elongation at Break [%] 9 8 9 8 8 14 14 Fiber- TR Strength
[MPa] -- -- -- -- -- 1830 1883 Reinforced Flexural Modulus [GPa] --
-- -- -- -- 63 68 Plastic Tube Fracture Strain [%] -- -- -- -- --
11 11 MR Strength [MPa] -- -- -- -- -- 1813 2080 Flexural Modulus
[GPa] -- -- -- -- -- 82 89 Fracture Strain [%] -- -- -- -- -- 8
9
[0258] As shown in Tables 3 and 4, each of the Example was superior
to Comparative Examples 1 and 2 without the component (C) in that
the resin plate was excellent in strength and elastic modulus,
while maintaining toughness. Moreover, the physical properties of
the fiber-reinforced plastic tube were improved in each of the
Examples as compared to Comparative Example 1 without the component
(C).
Examples 53 to 57, Comparative Examples 4 to 6
[0259] Curable resin compositions were prepared in the same manner
as in Example 1 except that the compositional ratios were changed
to those shown in Table 5, and resin plates, prepregs,
fiber-reinforced plastic plates, fiber-reinforced plastic tubes
were produced, on which various measurements and evaluations were
performed. The evaluation results are shown in Table 5.
TABLE-US-00005 TABLE 5 Composition (part by mass) Ex.53 Ex.54 Ex.55
Ex.56 Ex.57 Ex.58 Ex.59 Comp.Ex.4 Comp.Ex.5 Comp.Ex.6 Component(A)
jER4004P 50 0 0 0 0 0 0 0 0 0 jER4007P 0 50 50 50 50 22 22 0 0 0
Epoxy resin other jER1001 0 0 0 0 0 0 0 50 50 0 than jER1002 0 0 0
0 0 0 0 0 0 50 Component(A) Component(B) jER828 0 0 0 0 0 0 0 50 50
50 jER807 50 50 50 50 50 28 28 0 0 0 Component(H) TSR-400 0 0 0 0 0
50 50 0 0 0 Component(C) Dipentaerythritol 25 25 25 25 25 25 25 0
25 25 hexaacrylate Component (d1) 1400F 4.8 4.4 4.4 2.7 5.3 4.5 4.5
5.2 5.2 4.8 (D) DCMU-99 3.2 0 1 3 3 2.9 2.9 3.5 3.5 3.2 Omicure24 0
1.7 0 0 0 0 0 0 0 0 (d2) Di-t-hexyl peroxide 0.8 0.8 0.8 0.8 0.8 0
0 0 0.8 0.8 Dicumyl peroxide 0 0 0 0 0 0.4 0.8 0 0 0 Component(E)
VINYLEC E 0 0 0 0 0 3 3 0 0 0 Flexural Properties Flexural Strength
[MPa] 173 178 177 170 174 182 185 150 166 160 of Resin Plate
Flexural Modulus[GPa] 3.9 3.8 3.9 3.7 3.7 3.8 4 3.3 3.3 3.5
Elongation at Break[%] 10 7 7 9 8 8 9 14 9 14
INDUSTRIAL APPLICABILITY
[0260] The use of the curable resin composition of the present
invention enables production of an excellent fiber-reinforced
plastic tube. Therefore, the present invention can provide wide
variety of fiber-reinforced plastic molded articles with excellent
mechanical properties, ranging from, for example, molded articles
for sports and leisure applications such as golf club shafts, to
molded articles for industrial applications such as aircrafts.
* * * * *