JPS6399220A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having improved moldability such as curing properties, workability, etc., providing cured materials having excellent stability at high temperature and mechanical strength, containing a specific unsaturated ester, a monomaleimide compound and a specific styrene derivative. CONSTITUTION:The aimed composition containing (A) (i) an unsaturated ester compound obtained by reacting an epoxy compound (preferably cresol novolak type epoxy resin) containing two or more epoxy groups in one molecule with an unsaturated monobasic acid and, if necessary, a polybasic acid and/or (ii) an unsaturated ester compound obtained by reacting a compound (preferably cresol novolak) containing two or more phenolic hydroxyl groups in one molecule with a compound shown by formula I (R<1> and R<2> are H or methyl) containing epoxy shown by formula I (R<1> and R<2> are H or methyl) containing epoxy group and radically polymerizable unsaturated group in one molecule, (B) a monomaleimide compound and (C) a styrene derivative shown by formula II (R<3> is H or 1-4C alkyl).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a heat-resistant resin composition that has excellent moldability such as curability and workability, and provides a cured product with excellent stability and mechanical strength at high temperatures. It is about things.

(Prior Art and Problems to be Solved by the Invention) As resins with excellent stability under high temperatures, there are various heat-resistant resins represented by polyimide resins, polyamide-imide resins, and the like.

However, because these heat-resistant resins have high melting points, they require high temperatures or high pressures when molding, or require long periods of time under high temperatures and pressures for curing, or require special high-boiling point solvents to process the resins. Since it is necessary to use it by dissolving it, it has major problems in moldability, such as requiring a step of pressurizing or reducing the pressure above and below the IXX for a long period of time to remove the solvent. Therefore, it is extremely difficult to manufacture large-sized molded products using these heat-resistant resins or to continuously manufacture molded products using pultrusion molding, extrusion molding, or the like.

On the other hand, polyhydric phenol type epoxy resins such as bisphenol type epoxy resins and novolak type epoxy resins and (meth) resins with excellent moldability such as curability and workability.
Radically polymerizable resins such as epoxy (meth)acrylate or unsaturated polyester derived from acrylic acid are known, and these resins are usually blended with a radically polymerizable crosslinking agent such as styrene, and then converted to vinyl ester resin or Widely used as an unsaturated polyester resin. However, these resins do not necessarily reach a satisfactory level of thermal stability at high temperatures, which is a major obstacle in the development of new applications. desired.

The present inventors have discovered that radical polymerizable resin has excellent curability 1
The present invention was achieved as a result of various studies aimed at developing a resin that provides a cured product with high stability at high temperatures without impairing moldability such as workability or mechanical strength.

(Means and effects for solving the problems) The present invention has the following features:
Unsaturated ester (A) and/or 1 obtained by reacting an epoxy compound having two or more epoxy groups in one molecule with an unsaturated monobasic acid and, if necessary, a polybasic acid.
A compound having two or more phenolic hydroxyl groups in a molecule has an epoxy group and a radically polymerizable unsaturated bond in one molecule represented by the general formula (R and R are hydrogen or methyl groups independently of each other). and the unsaturated ester (8) obtained by reacting a compound having the monomaleimide compound (C) and the general formula (wherein, R3 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R4 is hydrogen or an alkyl group having 1 to 4 carbon atoms. 1
-5 alkyl group. ) The present invention relates to a heat-resistant resin composition containing a styrene derivative (D) represented by:

An epoxy compound having two or more epoxy groups in one molecule (hereinafter simply referred to as a polyfunctional epoxy compound) used to obtain the unsaturated ester (A) in the present invention.
For example, the general formula (where A is a CF3 alkylene group containing 1 to 4 carbon atoms, -C-, SO2, S or CF30, R5 is hydrogen or a methyl group, and X is hydrogen or halogen, and m is ○ or an integer in the range of 1 to 15.) Bisphenol type epoxy resin represented by the general formula (wherein R6 is hydrogen or a methyl group, R, R, R
9 represents hydrogen or an alkyl group, which may be the same or different, and n is an integer in the range of 1 to 15. ); glycidylamine type epoxy resins such as triglycidyl-p-aminophenol, triglycidyl-m-aminephenol, N-tetraglycidyl-diaminodiphenylmethane, polyglycidyl metaxylylene diamine; triglycidyl isocyanate; Examples include isocyanuric acid type epoxy resins such as nurate; tetrahydroxyphenylethane type epoxy resins; puntoin type epoxy resins; alicyclic epoxy resins; these can be used alone or in a mixture of two or more types.

Commercially available products include Araldite GY250, Araldite GY260, Araldite 6071, Araldite 8011, ECN1235, and ECN1235 manufactured by Ciba Geigy.
CN1235, ECN1235, ECN1273, EC
N1280, ECN1299, Araldite MY720
Epicote 828 and Epicote 10 manufactured by Nigel Chemical Co., Ltd.
01, Epicoat 1004; Dow Chemical Company glue, E
.

R, 330, D, E, R, 331, D, E, R.

662, D, E, R, 542, D, E, N, 431, D
, E, N, 438; Evotote YD- manufactured by Tobu Kasei ■
127, Evotote YD-011, Evotote YDB-
400, Evotote YDB-5001 Evotote YDF
-170, Evotote YDF-2001, YDCN-7
01, YDCN-702, YDCN-703, YDCN
-704, YDPN-638, YDPN-601, YD
PN-602, YDM-120, YH-434,5T-
110, etc. Furthermore, for example, glycidyl ether of a condensate of an unsaturated aldehyde and phenols, an adduct of a polyhydric phenol compound and an epoxy compound containing an average of two or more epoxy groups in one molecule, a polyhydric phenol and a monohydric phenol, etc. Although there are glycidyl etherified products of co-condensates of phenol, the polyfunctional epoxy compounds used in the present invention are not limited to these epoxy compounds; Any epoxy compound containing more than
These can be used alone or in combination of two or more.

Among these, it is particularly preferable to use a Talesol novolac type epoxy resin as the polyfunctional epoxy compound, since it is possible to obtain a resin composition that provides a cured product with particularly excellent heat resistance stability.

React with polyfunctional epoxy compound! ! l sum - salt v
! Examples of acids include half esters of unsaturated dibasic acids such as acrylic acid, methacrylic acid, crotonic acid, ()inamic acid, oleic acid, linoleic acid, linolic acid, maleic acid, and fumaric acid. These can be used alone or in combination of two or more.

In addition, examples of polybasic acids used as necessary in the present invention include maleic acid, fumaric acid, itaconic acid,
Unsaturated acids such as citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid,
Saturated acids such as trimellidic acid and pyromellitic acid, polybutadiene containing no carboxyl groups at both ends, butadiene-acrylonitrile copolymer having carboxyl groups at both ends, etc. can be used alone or in combination of two or more.

When reacting a polyfunctional epoxy compound with an unsaturated monobasic acid and, if necessary, a polybasic acid to obtain an unsaturated ester (8), an unsaturated monobasic acid is added per mole of epoxy group contained in the polyfunctional epoxy compound. The total carboxyl groups contained in the acid and the polybasic acid used as necessary are 0.7 to 1
．． It is used in a proportion of 3 mol, preferably 0.8 to 1.2 tl. In addition, when using a polybasic acid in combination with an unsaturated monobasic acid, it is best to keep the number of moles of the polybasic acid equal to or less than the number of moles of the unsaturated monobasic acid to develop excellent mechanical strength. preferred above.

The above esterification reaction is carried out in an inert solvent or without a solvent, heated to 60 to 150°C, preferably 70 to 130°C, and preferably in the presence of air.

Hydroquinones such as methylhydroquinone and hydroquinone to prevent gelation due to polymerization during the reaction;
It is preferable to use known and commonly used polymerization inhibitors such as benzoquinones such as p-benzoquinone and p-t-ruquinone.

Further, in order to shorten the reaction time, it is preferable to use an esterification catalyst, and examples of the esterification catalyst include, for example, N
, N-dimethylaniline, pyridine, triethylamine, hexamethylene diamine and other tertiary amines and their hydrochlorides or bromine-resistant salts; tetramethylammonium salts such as tetramethylammonium chloride and triethylbenzylammonium chloride; sulfonic acids such as valatoluenesulfonic acid; Sulfoxides such as dimethyl sulfoxide and methyl sulfoxide Sulfonium salts such as nitrimethylsulfonium chloride and dimethylsulfonium chloride; Phosphines such as triphenylphosphine and tri-n-butylphosphine: Lithium chloride, lithium bromide, tin chloride, chloride Known and commonly used metal halides such as zinc can be used.

As the inert solvent, toluene, xylene, etc. can be used, but since these solvents need to be removed after repulsion, it is preferable to use a styrene derivative (DJ) as the solvent.

A compound having two or more phenolic hydroxyl groups in one molecule (hereinafter simply referred to as a polyfunctional phenol compound) is used to obtain the unsaturated ester (8) in the present invention.

), for example, diphenolmethane (bisfe/-
F), diphenol ethane, diphenol propane (
Bisphenol A), diphenol sulfone (bisphenol S), 4.4'-thiobisphenol, 4.4'
-sulfinylbisphenol, 2,3'-oxybisphenol, bisphenol tetrachloride, bisphenol A tetrabromide, 1,1-bis-(4-hydroxyphenyl)-1-phenylethane, 1,1-bis-(4- Hydroxyphenyl)-1,1-dimethylmethane, phenol novolak, brominated phenol novolak, cresol novolak, brominated talesol novolak, resorcinol novolak, brominated resorcinol novolac, hydroquinone, (iso)cyanuric acid, methylresorcinol, etc. Can be done. Furthermore, there are also condensates of unsaturated aldehydes and phenols, adducts of polyhydric phenol compounds and epoxy compounds, co-condensates of polyhydric phenol compounds and 11-phenol compounds, and the like. The functional phenol compound is not limited to these, but any compound having two or more weakly acidic so-called phenolic hydroxyl groups in one molecule may be used, and these compounds can be used alone or in a mixture of two or more types. can.

Among these, it is particularly preferable to use cresol novolac as the polyfunctional phenol compound, since it is possible to obtain a resin composition that provides a cured product with particularly excellent heat resistance stability.

A compound having an epoxy group and a radically polymerizable unsaturated bond in one molecule (hereinafter simply referred to as an unsaturated glycidyl ester compound) to be reacted with a polyfunctional phenol compound.
is represented by the above general formula, and examples thereof include glycidyl methacrylate, glycidyl acrylate, 2-methylglycidyl methacrylate, and 2-methylglycidyl acrylate, and these can be used alone or in combination of two or more types.

To obtain the unsaturated ester (B) by reacting a polyfunctional phenol compound and an unsaturated glycidyl ester compound, a conventionally known ring-opening addition reaction may be followed. For example, phenolic water contained in the polyfunctional phenol compound The amount of unsaturated glycidyl ester compound is 0.5 to Jlil equivalent.
Blended at a ratio of 1.5 equivalents, preferably 0.8 to 1.2 equivalents, in an inert solvent or without a solvent, at 30 to 150°C.
The reaction is preferably carried out by heating to 50 to 130°C, preferably in the presence of air. In order to prevent gelation due to polymerization during the reaction, it is preferable to use known and commonly used polymerization inhibitors such as hydroquinones such as methylhydroquinone and hydroquinone; benzoquinones such as ρ-benzoquinone and p-torquinone.

Further, in order to shorten the reaction time, a ring-opening addition reaction catalyst can be used, and examples of the ring-opening addition reaction catalyst include tertiary amines such as triethylamine and triethylenediamine;
Amines such as dimethylaminoethanol and N-methylmorpholine; Quaternary ammonium salts such as triethylbenzylammonium chloride and trimethyldodecylammonium chloride; Imidazoles such as 2-ethylimidazole and 2-methyl-4-ethylimidazole;
Known and commonly used phosphines such as triphenylphosphine and tributylphosphine; tetraphenylboron salts such as triphenylphosphine tetraphenylborate and triethylamine tetraphenylborate; and metal halides such as zinc chloride and tin chloride are used. be able to.

As the inert solvent, for example, toluene, xylene, dimethylformamide, etc. can be used, but since these solvents need to be removed after the reaction, it is advantageous to use the styrene derivative (D) as the solvent.

Monomaleimide compound used in the present invention? +73(C)
Examples include N-methylmaleimide, N-ethylmaleimide, N-inpropylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-o-methylphenylmaleimide, N-
-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-1)
-Hydroxyphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-o-methoxyphenylmaleimide, N-o-carboxyphenylmaleimide-carboxyphenylmaleimide, N-0-chlorophenylmaleimide, N- m-
Examples include chlorophenylmaleimide and N-p-chlorophenylmaleimide, and these can be used alone or as a mixture of 2PIi or more.

The styrene derivative (D) used in the present invention is represented by the above general formula, and includes, for example, styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, o-(m or p-)methylstyrene. , o-(
m or p-) ethylstyrene, o- (m or p
-) iso-propylstyrene, o-(m or D-)
Examples include n-propylstyrene, o-(m or p-)n-butylstyrene, o-(m or I)-)t-butylstyrene, and these can be used alone or as a mixture of two or more types.

Among the styrene derivatives (D), styrene R L1 form (
When using an alkyl group-substituted styrene in which R4 in the general formula representing D) is an alkyl group having 1 to 5 carbon atoms, a resin composition that provides a cured product with particularly excellent heat resistance stability can be obtained, which is particularly preferred. .

Furthermore, among the alkyl group-substituted styrenes, o-
(m or p-)methylstyrene is preferred.

The resin composition of the present invention comprises an unsaturated ester (A) and/or
Or unsaturated ester (8) and monomaleimide compound (
C) and a styrene derivative (D) as essential components, but in addition to these components, other polymerizable crosslinking agents may be contained as necessary.

Examples of these polymerizable crosslinking agents include divinylbenzene, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, tricyclodecenyl (meth)acrylate,
Trimethylolpropane tri(meth)acrylate, diethylene glycol di(meth)acrylate, 1,4-
Butanediol di(meth)acrylate, tris(2-
hydroxyethyl) isocyanuric acid (meth)acrylic acid ester, 2,2-bis(4-(2-and droxyethyl)phenyl)propane di(meth)acrylate, etc.
Those that easily copolymerize with any of the unsaturated ester (8), the unsaturated ester (B), the monomaleimide compound (C), and the styrene derivative (D) are preferred, and these may be used alone or as a mixture of two or more types. Can be done. However, if these polymerizable crosslinking agents are used too much, the stability of the resulting cured product of the resin composition at high temperatures will decrease, so care must be taken.

Unsaturated ester (A) and/or unsaturated ester (
B), monomaleimide compound (C), and styrene derivative (D) are not particularly limited, but from the viewpoint of mechanical properties and heat resistance, unsaturated ester (A) and/or unsaturated ester (B) ) 35-90% weight, molded maleimide compound (C) 5-40%, styrene derivative (D) 5-60% (however, (A), (B)
, (C) and (D) components is 100%. ) is desirable.

If the blending ratio of the monomaleimide compound (C) is less than 5% by weight, there will be little effect on stability under high temperatures, and even if the blending ratio exceeds 40% by weight, the monomaleimide compound (C) There is no longer any improvement in stability at high temperatures due to an increase in monomaleimide compounds (
As a result of insufficient dissolution of C), the mechanical strength of the cured product may decrease. Also. If the blending ratio of the styrene derivative (D) is less than 5 molding percent, the viscosity of the resin composition will increase, and the curability will also decrease, and the workability of the resulting resin composition will not only decrease, but also the curing of the resulting resin composition will decrease. The stability of the product at high temperatures also decreases. Moreover, if the amount exceeds 60% by weight and is added in large quantities, the mechanical strength of the cured product will decrease, which is not preferable.

As a method for curing the resin composition of the present invention, a photopolymerization method using a photosensitizer, a heat polymerization method using an organic peroxide or an azo compound, a room temperature polymerization method using an organic peroxide and an accelerator, etc. can be used. can.

Examples of photosensitizers include benzoin, benzoin methyl ether, and benzoin ethyl ether.

There are many known compounds such as carbonyl compounds such as benzoin propyl ether, benzoin isobutyl ether, and benzophenone, and sulfur compounds such as diphenyl disulfide. Can also be used in combination with

Examples of organic peroxides include t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, and penzoyl peroxide.

Cyclohexanone peroxide, methyl ethyl ketone peroxide, acetoacetate peroxide,
Examples include bis-4-t-butylcyclohexyl peroxydicarbonate, and known azo compounds such as azobisisobutyronitrile may be used alone or in combination with 2f! The above mixtures can be used.

As the accelerator, known ones such as salts of polyvalent metals such as salts of octylic acid and naphthenic acid such as cobalt, iron, and manganese, and organic amines such as dimethylaniline, diethylaniline, p-toluidine, and ethanolamine may be used. Alternatively, two or more types can be used in combination.

Further, the resin composition of the present invention may include glass t.
HIft, carbon fiber, aramid $11. Reinforcing materials such as whiskers, powdered reinforcing agents, fillers, thickeners, silane coupling agents such as acrylic silane, mold release agents such as calcium stearate and paraffin, pigments and coloring agents, flame retardants and flame retardants, etc. Can be blended. Furthermore, if desired, thermoplastic resins, elastomers, unsaturated polyester resins, etc. can be blended within a range that does not impede the object of the present invention.

(Effects of the Invention) The heat-resistant resin composition of the present invention has excellent curability, can be cured in a very short time by photopolymerization or heat polymerization, and can be cured even at room temperature. Moreover, the cured product obtained by curing has not only the excellent properties inherent to vinyl ester resin in terms of water resistance, chemical resistance, and mechanical strength, but also
It has excellent stability at high temperatures, a property not found in conventional heat-resistant resins. Taking advantage of these advantages, the resin composition of the present invention can be used as a resin for large molded products with excellent stability under high temperatures by, for example, contact pressure molding or filament winding, or extrusion molding, pultrusion molding, etc. ! Sheet molding compound (S
MG) and bulk molding compound (BMG)
It is suitable for composite materials such as industrial resins, and examples of its application include corrosion-resistant equipment such as tanks, pipes, ducts, and scrubbers, leaf springs, and drive shafts.

Examples include automotive parts such as wheels, electrical and electronic parts such as printed wiring boards and various insulating parts, and coating materials for optical fiber cables.

(Examples) Hereinafter, the present invention will be specifically explained by examples, but the present invention is not limited to the following examples. In addition, all parts and percentages below are based on weight.

Example 1 88 parts of methacrylic acid, cresol novolac epoxy resin ECN-1280 (manufactured by Ciba Geigy, Inc.,
227 parts of epoxy (containing an average of 5.1 epoxy groups in 227.1 molecules), 88.5 parts of styrene, 0.246 parts of hydroquinone, and 1.13 parts of triethylamine were added, and while stirring under a stream of air, 115 parts of epoxy C. for 8 hours to obtain an unsaturated ester with an acid value of 6 as a styrene solution, and 88.5 parts of styrene was added to the solution to obtain an unsaturated ester resin (a). The obtained unsaturated ester resin (a
) and 20 parts of N-phenylmaleimide were mixed,
A resin composition (1) was obtained.

Example 2 Into the same reaction vessel used in Example 1, 88% of methacrylic acid was added.
8 parts, phenol novolac epoxy resin, E, N,
438 (manufactured by Dow Chemical Company, epoxy equivalent: 178.1
Containing an average of 3.6 epoxy groups in the molecule) 178 parts,
75 parts of styrene, 0.2 parts of hydroquinone and 0.96 parts of trimethylbenzylammonium chloride were charged and heated at 115°C for 7 hours with stirring under a stream of air to obtain an unsaturated ester with an acid value of 5.5 as a styrene solution. , further added 75 parts of styrene to form an unsaturated ester resin (
b) was obtained. Obtained unsaturated ester resin (b) 100
and 20 parts of N-phenylmaleimide were mixed therein to obtain a resin composition (2).

Example 3 15 parts of N-cyclohexylmaleimide and 10 parts of tris(2-hydroxyethyl)isocyanuric acid acrylate were mixed with 100 parts of the unsaturated ester resin (a) obtained in Example 1, and the tree weight Phase acid product (3) was obtained.

Example 4 Into the same reaction vessel as used in General Example 1, 88% of methacrylic acid was added.
8 parts, bisphenol type epoxy resin Araldite GY
250<Ciba Geigy, epoxy ff1185)
185 parts of hydroquinone, 0.084 parts of hydroquinone, and 1.0 part of triedylamine were charged and heated at 115° C. for 6 hours with stirring under a stream of air to obtain an unsaturated ester with an acid value of 7. 65 parts of this unsaturated ester and 35 parts of styrene were mixed to obtain an unsaturated ester resin (C). 30 parts of N-phenylmaleimide was mixed with 100 parts of the obtained unsaturated ester resin (c) to obtain a resin composition (4).

Example 5 Into the same reaction vessel as used in Example 1, 103 parts of phenol novolac (softening point 85°C, 0t] equivalent weight 103),
142 parts of glycidyl methacrylate.

66 parts of styrene, 0.2 parts of methylhydroquinone and 0.85 parts of triethylamine were charged and heated at 115°C for 8 hours with stirring under a stream of air, and glycidyl methacrylate was completely reacted according to the nuclear magnetic resonance absorption spectrum of the reactants. After confirming this, 66 parts of α-methylstyrene was added to the colander to obtain unsaturated ester tree 11R(d).

25 parts of N-cyclohexylmaleimide was mixed with 100 parts of the obtained unsaturated ester resin (d), and the resin composition (5
) was obtained.

Example 6 Into the same reaction vessel as used in Example 1, 120 parts of cresol novolac (softening point 100°C, OH equivalent 120),
128 parts of glycidyl acrylate.

65 parts of styrene, 0.18 parts of p-benzoquinone and 1.15 parts of triethylbenzylammonium chloride were charged and heated at 110°C for 9 hours with stirring under a stream of air, and glycidyl acrylate was determined by nuclear magnetic resonance absorption spectrum of the reactants. After confirming complete reaction, 30 parts of styrene and 40 parts of trimethylolpropane trimethacrylate were added to form the unsaturated ester resin (e).
(q) 25 parts of Nm-methylphenylmaleimide was added to 100 parts of the obtained unsaturated ester resin (e) to obtain a resin composition (6).

Example 7 In the same reaction vessel used in Example 1, 80% of methacrylic acid was added.
8 parts, Talesol novolac epoxy resin ECN-12
80 (manufactured by Ciba Geigy, epoxy ff1227) 2
27 parts of p-methylstyrene, 88.5 parts of p-methylstyrene, 0.246 parts of hydroquinone, and 1.13 parts of triethylamine were heated at 110°C for 10 hours with stirring under a stream of air to obtain 1filli7 parts of p-methylstyrene solution.
．． An unsaturated ester of No. 5 was obtained, and 88.5 parts of p-methylstyrene was added to obtain an unsaturated ester resin of No. 11.

10 parts of N-o-methylphenylmaleimide was mixed with 100 parts of the obtained unsaturated ester resin [) to prepare a resin composition (
7)

Example 8 20 parts of N-phenylmaleimide was mixed with 100 parts of the unsaturated ester resin ([) obtained in Example 7 to obtain a resin composition (8).

Example 9 In the same reaction vessel used in Example 1, acrylic acid 36
parts, 43 parts of methacrylic acid, liquid rubber containing carboxyl groups at both ends Hycar CTBN 1300 x 8 (B
, F, manufactured by Gutdrich Co., Ltd., butadiene-acrylonitrile copolymer containing both terminal carboxyl groups) 30 parts, cresol novolak epoxy resin EOCN-1020 (manufactured by Nippon Kayaku ■, epoxy Toichi 203) 203 parts, vinyltoluene 128 parts, triethyl 1.2 parts of benzylammonium chloride and 0.26 parts of methylhydroquinone were charged and heated at 115°C for 8 hours with stirring under a stream of air to obtain an unsaturated ester with an acid value of 6.2 as a vinyl toluene solution. 80 parts of toluene was added to obtain an unsaturated ester resin ((1). 100 parts of the obtained unsaturated ester resin (1) was mixed with 25 parts of N-cyclohexylmaleimide to obtain a resin composition (9). I got it.

Example 10 In the same reaction vessel used in Example 1, 88% of methacrylic acid was added.
8 parts, bisphenol type epoxy resin Evototo YDF
-170 (manufactured by Toto Kasei ■, epoxy equivalent: 170) 170
1 part, 0.07 parts of hydroquinone and 1.1 parts of triethylpentylammonium chloride were heated at 115°C for 6 hours with stirring under a stream of air to obtain an unsaturated ester with an acid value of 8, and further 110 parts of vinyltoluene. was added to obtain an unsaturated ester resin (h). 20 parts of N-phenylmaleimide was mixed with 100 parts of the obtained unsaturated ester resin (h) to obtain a resin composition (10).

Example 11 In the same reaction vessel as used in Example 1, 120 parts of cresol novolac (softening point 100°C, OH equivalent 120),
142 parts of glycidyl methacrylate, 7 parts of vinyltoluene
0 parts, 0.24 parts of methylhydroquinone, and 1.0 parts of triethylamine were heated at 115°C for 8 hours with stirring under a stream of air, and the nuclear magnetic resonance absorption spectrum of the reactants showed that glycidyl methacrylate had completely reacted. Confirm and add 70 parts of vinyltoluene.
An unsaturated ester resin (i) was obtained. 20 parts of N-phenylmaleimide was mixed with the obtained unsaturated ester resin uzoo part to obtain a resin composition (11).

Example 12 Unsaturated ester resin (1) obtained in Example 11 100
15 parts of N-cyclohexylmaleimide and 10 parts of tris(2-hydroxyethyl)isocyanuric acid acrylic acid ester were mixed into the resulting resin composition to obtain a resin composition (12).

Example 13 In the same reaction vessel as used in Example 1, 103 parts of phenol novolak (softening point 85°C, OH ff1103) and 142 parts of glycidyl methacrylate were added.

66 parts of vinyltoluene, 0.2 parts of methylhydroquinone, and 1.0 parts of triethylbenzylammonium chloride.
13 parts of glycidyl methacrylate was charged and heated at 110°C for 10 hours with stirring under a stream of air. After confirming complete reaction of glycidyl methacrylate by nuclear magnetic resonance absorption spectrum of the reactant, 66 parts of vinyltoluene was added to A saturated ester resin (j) was obtained. 20 parts of N-phenylmaleimide was mixed with 100 parts of the obtained unsaturated ester resin (j) to obtain a resin composition (13).

Example 14 Into the same reaction vessel as used in Example 1, 103 parts of phenol novolak (softening point 85°C, OH ff1103) and 142 parts of glycidyl methacrylate.

66 parts of p-methylstyrene, 0.0 parts of methylhydroquinone.
2 parts and 1.13 parts of triethylbenzylammonium chloride were added, and the mixture was heated to 110% while stirring under an air stream.
℃ for 10 hours, confirming complete reaction of glycidyl methacrylate by nuclear magnetic resonance absorption spectrum of the reactant, and adding 66 parts of p-methylstyrene to the colander.
An unsaturated ester resin (k) was obtained. 15 parts of N-cyclohexylmaleimide was mixed with 100 parts of the obtained unsaturated ester resin (k) to obtain a resin composition (14).

Comparative Example 1 The unsaturated ester resin (b) obtained in Example 2 was used as it was to prepare a comparative resin composition (1).

Comparative Example 2 15 parts of tris(2-hydroxyethyl)isocyanuric acid acrylate were mixed with 100 parts of the unsaturated ester resin (b) obtained in Example 2 to obtain a comparative resin composition (2).

Comparative Example 3 The unsaturated ester resin (e) obtained in Example 6 was used as it was to prepare a comparative resin composition (3).

Comparative Example 4 The unsaturated ester resin (i) obtained in Example 11 was used as it was to prepare a comparative resin composition (4).

Comparative Example 5 100 parts of the unsaturated ester resin (i) obtained in Example 11 was mixed with 10 parts of tris(2-hydroxyethyl)isocyanuric acid acrylate to obtain a comparative resin composition (5).

Application Examples 1 to 14 and Comparative Application Examples 1 to 5 Examples 1 to 14
and resin compositions (1) to (1) obtained in Comparative Examples 1 to 5.
4) and comparative resin compositions (1) to (5) each at 100%
After adding 1 part of t-butylperoxy-2-ethylhexanoate to 1 part of t-butylperoxy-2-ethylhexanoate and mixing well, a 201 square satin weave glass cloth YES-2101-N-1 (Nippon Glass 11
11ift4! If), 12 Bliss were superimposed and pressed for 3 minutes at 120° C. with 1307 (Si/ci) to obtain a V4 laminate with a glass content of 65 ± 1% and a thickness of 3 HR. After curing the laminate by further heating it in an air oven at 180° C. for 1 hour, it was used for evaluation of thermal stability.

The evaluation results are summarized in Table 1.

Thermal stability was evaluated by using a 75'' x 25'' x 3'' laminate test piece and determining the heating weight loss rate and the bending strength retention rate after heating using the following formula.

The bending strength was measured in accordance with JIS K 6911.

Heating weight loss rate (%) - Glass! The I fiber concavity was measured by heating the test piece in air at 240°C for 500 hours and then heating it at 600°C for 5 hours.

Bending strength retention rate (%) − 240℃-500 hours air initial bending strength Chapter 1 Table

Claims (1)

[Claims] 1. An unsaturated ester (A) obtained by reacting an epoxy compound having two or more epoxy groups in one molecule with an unsaturated monobasic acid and, if necessary, a polybasic acid. Or, a compound having two or more phenolic hydroxyl groups in one molecule has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (However, R^1 and R^2 are hydrogen or methyl groups, regardless of each other.) Unsaturated ester (B) obtained by reacting a compound having an epoxy group and a radically polymerizable unsaturated bond in one molecule represented by, monomaleimide compound (C), and general formula ▲ Numerical formula, chemical formula, table, etc. Contains a styrene derivative (D) represented by ▼ (However, R^3 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R^4 is hydrogen or an alkyl group having 1 to 5 carbon atoms.) A heat-resistant resin composition made of 2. The heat-resistant resin composition according to claim 1, wherein the epoxy compound having two or more epoxy groups in one molecule is a cresol novolac type epoxy resin. 3. The heat-resistant resin composition according to claim 1, wherein the compound having two or more phenolic hydroxyl groups in one molecule is cresol novolak. 4. The heat-resistant resin composition according to claim 1, wherein R^4 in the general formula representing the styrene derivative (D) is an alkyl group having 1 to 5 carbon atoms.