JPH06157716A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin composition produced by dissolving a specific copolymer in an organic solvent, having easy curability and excellent heat-resistance, mechanical properties, chemical resistance, adhesivity, processability, optical properties, smoothness and flatness and useful as an optical device, etc. CONSTITUTION:This resin composition is produced by dissolving (A) 100 pts.wt. of a copolymer consisting of (i) preferably <=30wt.% of an unsaturated carboxylic acid (anhydride) such as acrylic acid, (ii) preferably 20-50wt.% of a radically polymerizable compound containing epoxy group such as glycidyl acrylate, (iii) preferably 20-50wt.% of a monoolefinic unsaturated compound such as methyl methacrylate and preferably further (iv) preferably 5-15wt.% of a conjugated diolefinic unsaturated compound such as 1,3-butadiene in (B) preferably 100-400 pts.wt. of an organic solvent such as methanol and THF.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition, and more specifically, it is easily cured by heating without using a special curing agent, and has heat resistance, mechanical properties, chemical resistance and adhesion. The present invention relates to an optical device capable of forming a coating film (cured film) having excellent properties, processability, optical characteristics, smoothness and flatness, and an epoxy thermosetting resin composition for semiconductors.

[0002]

2. Description of the Related Art Conventionally, a thermosetting resin composition based on an epoxy resin has a heat resistance of a resin obtained after curing,
Due to its excellent mechanical properties, chemical resistance, adhesiveness, processability and optical properties, it is used for paints, electrical insulation materials, printed wiring boards, adhesives, civil engineering and construction, jigs and tools, molding materials, sealing resin materials. Widely used for such purposes.

This epoxy resin does not easily undergo a sufficient curing reaction by itself, and conventionally, in order to form a cured film from the epoxy resin, a special curing agent is added to the epoxy resin to cure it, or the epoxy resin is cured. Is modified with another resin or a carboxylic acid, and the epoxy resin itself is cured with the curability.

[0004]

However, the above-mentioned conventional epoxy resin has various problems.

That is, when the epoxy resin is cured with a special curing agent, the compatibility between the epoxy resin and the curing agent and the storage stability are poor, and the workability is poor.

On the other hand, in the case of a modified epoxy resin obtained by modifying an epoxy resin with a carboxylic acid or the like, it is difficult to adjust the modification amount during modification, and the modification reaction is complicated and the quantitativeness of the reaction (unreacted to the product (Influence of substances, side reactions, etc.)
There was a problem in quality control that it was inferior to. In addition, when the modified epoxy resin is produced, there is a problem that the epoxy group and the carboxylic acid group react with each other to crosslink and the polymerization system gels.

Further, with the conventional epoxy resin, it is difficult to flatten the substrate used (hereinafter referred to as "base substrate"). Therefore, in general, when forming a flat coating film using an epoxy resin, the substrate surface is preliminarily flattened to some extent with a low-viscosity and high-concentration material, and then the epoxy resin is applied to form A flattened cured film was obtained. However, if an attempt is made to obtain a flattened cured film by such a method, the work will be complicated and the resulting cured film will be expensive.

Therefore, in addition to having the excellent properties inherent to epoxy resins, they also have excellent storage stability and workability, as well as gloss, flatness of the underlying substrate, and the surface of the coating film itself. It has been desired to develop an epoxy thermosetting resin composition that allows a cured film having excellent smoothness to be easily obtained.

[0009]

The first thermosetting resin composition according to the present invention comprises [A-1] (a-1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, a-2) A copolymer of an epoxy group-containing radically polymerizable compound and (a-3) a monoolefin unsaturated compound is dissolved in [B] an organic solvent.

The second thermosetting resin composition according to the present invention is [A-2] (a-1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, and (a-2) epoxy. A copolymer of a group-containing radically polymerizable compound, (a-3) a monoolefinic unsaturated compound, and (a-4) a conjugated diolefinic unsaturated compound is dissolved in an organic solvent [B]. Is characterized by.

The thermosetting resin composition according to the present invention contains a copolymer having both an epoxy group and a carboxylic acid group, and is easily cured by heating without using a specific curing agent. Such a thermosetting resin composition according to the present invention has excellent properties inherent to an epoxy resin, and also has excellent storage stability and workability. It is possible to easily obtain a cured film having excellent flatness of the substrate and smoothness of the coating film itself.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The thermosetting resin composition according to the present invention will be described below. The copolymer used in the present invention is (a-1) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, (a-2) a radically polymerizable compound having an epoxy group, and (a-3) A copolymer [A-1] with a mono-olefin unsaturated compound, or (a-1) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, and (a-2) a radical having an epoxy group It is a copolymer [A-2] of a polymerizable compound, (a-3) a monoolefinic unsaturated compound, and (a-4) a conjugated diolefinic unsaturated compound.

Specific examples of the unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (a-1) include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, maleic acid and fumaric acid. Preferred are dicarboxylic acids such as citraconic acid, mesaconic acid and itaconic acid, and anhydrides of these dicarboxylic acids.

Of these, acrylic acid, methacrylic acid and maleic anhydride are preferably used. As the radically polymerizable compound having an epoxy group (a-2), for example, glycidyl acrylate, glycidyl methacrylate,
α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,
4-epoxy butyl, -6,7-epoxy heptyl acrylate, -6,7-epoxy heptyl methacrylate, -6,7-epoxy heptyl α-ethyl acrylate and the like can be mentioned.

Of these, glycidyl acrylate, glycidyl methacrylate, and 6,7-epoxyheptyl methacrylate are preferably used. These may be used alone or in combination.

Examples of the monoolefin unsaturated compound (a-3) include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate, methyl acrylate and isopropyl. Acrylic alkyl esters such as acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyloxyethyl methacrylate, methacrylic acid cyclic alkyl esters such as isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl Acrylic acid cyclic alkyl ester such as acrylate, dicyclopentaoxyethyl acrylate, isobornyl acrylate Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate, acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate, dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid, 2-hydroxyethyl methacrylate, 2-hydroxy Hydroxyalkyl ester such as propyl methacrylate, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Examples thereof include vinyl acetate.

Of these, styrene, dicyclopentanyl methacrylate and p-methoxystyrene are preferred. These may be used alone or in combination.

Further, a conjugated diolefin unsaturated compound (a-
Examples of 4) include 1,3-butadiene, isoprene, and 2,3-dimethylbutadiene. These may be used alone or in combination.

The copolymer [A-1] consisting of the constitutional units derived from each of the above components is represented by the following formulas (1) to (5)
A copolymer comprising a structural unit represented by is preferred. Further, the copolymer [A-2] is preferably a copolymer composed of structural units represented by the following formulas (1) to (6),
(1), (3), (4), (5), a copolymer consisting of constitutional units represented by (6) and the formula (2), (3), (4), (5), (6 A copolymer composed of a structural unit represented by

The formulas (1) and (2) are structural units derived from an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride (a-1), respectively, and the formula (3) is a radical having an epoxy group. The polymerizable compound (a-2) is a structural unit derived from the formula (4) and (5) is a structural unit derived from a monoolefin unsaturated compound (a-3), the formula (6 ) Is a structural unit derived from a conjugated diolefin unsaturated compound (a-4).

[0021]

[Chemical 1]

(In the formula, R ¹ is a hydrogen atom or a lower alkyl group.)

[0023]

[Chemical 2]

(In the formula, R ¹ is a hydrogen atom or a lower alkyl group, and n is an integer of 1 to 10.)

[0025]

[Chemical 3]

(In the formula, R ¹ is a hydrogen atom or a lower alkyl group.)

[0027]

[Chemical 4]

(In the formula, R ¹ is a hydrogen atom or a lower alkyl group, R ² is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms, and this cycloalkyl group is a substituent group. May have.)

[0029]

[Chemical 5]

(In the formula, R ³ is a hydrogen atom or a lower alkyl group.) The copolymer [A-1] or [A-2] used in the present invention is the above unsaturated carboxylic acid or And / or the structural unit derived from unsaturated carboxylic acid anhydride (a-1) is contained in an amount of preferably 40% by weight or less, particularly preferably 30% by weight or less.

The copolymer [A-1] or [A-2] used in the present invention comprises a structural unit derived from the radically polymerizable compound (a-2) having an epoxy group, preferably 10 to
It is contained in an amount of 70% by weight, particularly preferably 20 to 50% by weight.

The copolymer [A-1] or [A-2] used in the present invention preferably comprises 10 to 70% by weight of a structural unit derived from the monoolefin unsaturated compound (a-3). , Particularly preferably in an amount of 20 to 50% by weight.

Further, the copolymer [A-2] used in the present invention
Is a structural unit derived from a conjugated diolefin unsaturated compound (a-4), 3 to 30% by weight, particularly preferably 5 to
It is contained in an amount of 15% by weight.

By the way, when the copolymer is produced only from the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride (a-1) and the epoxy group-containing radically polymerizable compound (a-2), the epoxy group and the carboxylic acid are used. The acid group may react with each other and crosslink to cause gelation of the polymerization system.

On the other hand, the copolymer [A-1] or [A-2] used in the present invention has an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride (a-1) and an epoxy group. In addition to the radically polymerizable compound (a-2) monoolefin unsaturated compound (a-3) and conjugated diolefin unsaturated compound (a-4) is copolymerized in the amount as described above, The epoxy group reacts with the carboxylic acid group to prevent the polymerization system from gelling, and the storage stability is excellent.

Copolymer [A-1] having such a composition
Alternatively, the thermosetting resin composition containing [A-2] can form a cured film having excellent heat resistance. The radical-polymerizable compound (a-2) having an epoxy group in the copolymer [A-1] or [A-2] is less than 10% by weight or the monoolefin unsaturated compound (a-3) ) 7 units
If it exceeds 0% by weight, the heat resistance of the cured film obtained from the thermosetting resin composition containing these copolymers [A-1] or [A-2] may decrease.

Further, a conjugated diolefin unsaturated compound (a-
The thermosetting resin composition containing the copolymer [A-2] containing the structural unit derived from 4) in the above amount can flatten the level difference on the underlying substrate to a higher degree.

When the copolymer [A-1] or [A-2] contains more than 30% by weight of the structural unit derived from the conjugated diolefin unsaturated compound (a-4), The heat resistance of the cured film obtained from the thermosetting resin composition containing these copolymers [A-1] or [A-2] may decrease.

The above-mentioned copolymers [A-1] and [A-
2] is soluble in alkaline aqueous solution. The above-mentioned copolymers [A-1] and [A-2] can be produced only by the copolymerization step without the modification step. Such a copolymer [A-1] or [A-2] has the above-mentioned (a-
1) Unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a-2) Radical polymerizable compound having epoxy group, (a-3) Monoolefin unsaturated compound and / or (a-4) Conjugated The diolefin unsaturated compound can be obtained by radical polymerization in a solvent in the presence of a catalyst (polymerization initiator).

Examples of the solvent used at this time include alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, cellosolve esters such as methyl cellosolve acetate, aromatic hydrocarbons,
Examples thereof include ketones and esters.

As the catalyst, those generally known as radical polymerization initiators can be used. For example, 2,2 '
-Azobisisobutyronitrile, 2,2'-azobis- (2,4-
Azo compounds such as dimethyl valeronitrile) and 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, 1,1'-bis- (T-
Examples include organic peroxides such as butylperoxy) cyclohexane and hydrogen peroxide.

When a peroxide is used as the radical polymerization initiator, it may be used as a redox type initiator by using the peroxide together with a reducing agent. The above copolymer [A-
1] or [A-2] has a molecular weight and its distribution as long as the solution of the composition of the present invention can be uniformly applied.
It is not particularly limited.

The thermosetting resin composition according to the present invention comprises the above copolymer [A-1] or [A-2] dissolved in the organic solvent [B].

The thermosetting resin composition according to the present invention is
The copolymer [A-1] and the copolymer [A-2] may be used in combination. As the organic solvent used in the present invention, those which can uniformly dissolve the copolymer [A-1] or [A-2] and which do not react with these are used.

Examples of such a solvent include alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, methyl cellosolve acetate and ethyl cellosolve acetate. Ethylene glycol alkyl ether acetates, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether and other diethylene glycols, propylene glycol methyl ether acetate, propylene glycol propyl ether acetate and other propylene glycol alkyl ether acetates, toluene, xylene and other fragrances Group hydrocarbons , Methyl ethyl ketone, cyclohexanone, ketones such as 4-hydroxy-4-methyl-2-pentanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, Ethyl ethoxyacetate, ethyl hydroxyate, methyl 2-hydroxy-3-methylbutanoate, 3
Esters such as -methyl methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl acetate and butyl acetate can be mentioned.

Further, together with these, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether, dihexyl Ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, A high boiling point solvent such as phenyl cellosolve acetate can also be used.

Among these solvents, glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, and 2-hydroxypropionic acid are used because of their solubility and reactivity with each component. Esters such as ethyl and diethylene glycols such as diethylene glycol monomethyl ether are preferably used.

These may be used alone or in combination. In the thermosetting resin composition according to the present invention,
The organic solvent [B] is the above copolymer [A-1] or [A-2].
It is used in an amount of 100 to 500 parts by weight, preferably 100 to 400 parts by weight, based on 100 parts by weight.

The thermosetting resin composition according to the present invention can be easily cured by heating without using a special curing agent. Moreover, this thermosetting resin composition is excellent in storage stability and workability.

The thermosetting resin composition according to the present invention has heat resistance, mechanical properties, chemical resistance, adhesiveness, processability,
A cured film having excellent optical characteristics and smoothness can be formed.

The thermosetting resin composition according to the present invention may contain components other than the above components, if necessary, within a range not impairing the object of the present invention.

As such other component, a surfactant may be mentioned. As the surfactant, for example, BM-1
000, BM-1100 (manufactured by BM Chemie), Megafac F142D, F172, F173, F183.
(Manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-
135, FC-170C, FC-430, FC-
431 (Sumitomo 3M Limited), Surflon S-1
12, the same S-113, the same S-131, the same S-141, the same S-145 (manufactured by Asahi Glass Co., Ltd.), SH-28PA, the same-
190, ibid-193, SZ-6032, SF-8428
Fluorine-based surfactants marketed under the names such as (Toray Silicone Co., Ltd.) can be used.

These surfactants are preferably used in an amount of 5 parts by weight or less, more preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the copolymers [A-1] and [A-2]. Used.

Further, an adhesion aid may be used to improve the adhesion to the substrate. As the adhesion aid, a functional silane coupling agent is preferable. Here, the functional silane coupling agent includes a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group, and more specifically, trimethoxysilylbenzoic acid, γ -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Examples include silane.

These adhesion assistants can be used alone or in combination of two or more kinds. The adhesion aid is preferably 20 parts by weight or less, more preferably 0.05 to 1 with respect to 100 parts by weight of the copolymers [A-1] and [A-2].
Used in an amount of 0 parts by weight.

Formation of coating film (cured film) A desired coating film can be formed by applying the thermosetting resin composition as described above on the surface of a substrate and removing the solvent by heating. The method of coating the surface of the substrate is not particularly limited, and various methods such as a spray method, a roll coating method and a spin coating method can be adopted.

The coating film formed as described above is usually heated by a heating device such as a hot plate or an oven to 150-150.
A cured film is obtained by heating at a temperature of 250 ° C. for a predetermined time. For example, by heating on a hot plate for 5 to 30 minutes and in an oven for about 30 to 90 minutes, the heat resistance, transparency, hardness, etc. are excellent, and the steps of the underlying substrate can be flattened to a higher degree.

[0058]

EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

In the examples,% means% by weight unless otherwise specified.

[0060]

Example 1 Synthesis of Copolymer After a flask equipped with a dry ice / methanol reflux was replaced with nitrogen, 2,2′-azobisisobutyronitrile was used.
459.0 g of a diethylene glycol dimethyl ether solution in which 0 g was dissolved was charged. Styrene 22.
5 g, methacrylic acid 45.0 g, dicyclopentanyl methacrylate 45.0 g, glycidyl methacrylate 9
After charging 0.0 g and 22.5 g of 1,3-butadiene, gentle stirring was started. The temperature of the solution was raised to 80 ° C. and kept at this temperature for 5 hours.

Thereafter, the obtained reaction product was dropped into a large amount of methanol to solidify the reaction product. This coagulated product was washed with water, redissolved in 200 g of tetrahydrofuran, and coagulated again with a large amount of methanol. This redissolving-coagulation operation was performed three times in total, and the obtained coagulated product was vacuum dried at 40 ° C. for 48 hours to obtain the target copolymer (1).

Preparation of Thermosetting Resin Composition 25 g of the above-mentioned copolymer (1) was dissolved in 75 g of diethylene glycol dimethyl ether and then filtered using a 0.22 μm Millipore filter to obtain the thermosetting resin composition (1).
Was prepared.

(I) Formation of coating film The composition (1) was applied onto a SiO ₂ glass substrate using a spinner and then heat-treated at 180 ° C. for 30 minutes on a hot plate to give a film thickness of 2. A 0 μm coating film was formed.

(Ii) Evaluation of Transparency In the above (i), except that Corning 7059 (manufactured by Corning) was used instead of the SiO ₂ glass substrate,
A coating film was formed in the same manner as (i).

The transmittance of the substrate on which the coating film was formed as described above was measured at 400 to 800 nm using a spectrophotometer (150-20 type table beam, Hitachi Ltd.).
At this time, when the minimum transmittance exceeds 98%, it is set as ◯, and 9
The case of 5 to 98% was marked with Δ, and the case of less than 95% was marked with x.

The results are shown in Table 1. (iii) Evaluation of heat resistance Using the substrate on which the coating film was formed in (i) above, 250
The sample was heated on a hot plate at a temperature of 1 ° C. for 1 hour, and the heat resistance was evaluated by the rate of change in film thickness (remaining film rate) before and after heating.

When the residual film ratio exceeds 98%, it is designated as ◯, and 9
The case of 5 to 98% was marked with Δ, and the case of less than 95% was marked with x. The results are shown in Table 1.

(Iv) Evaluation of heat discoloration resistance Using the substrate on which the coating film was formed in (i) above, 250
The sample was heated on a hot plate at ℃ for 1 hour, and the thermal discoloration resistance was evaluated by the change in transmittance. When the rate of change at this time is less than 5%, it is ◯, and when it is 5-10%, it is Δ,
The case where it exceeded 10% was marked with x.

The transmittance was determined in the same manner as (ii) Transparency evaluation.

The results are shown in Table 1. (v) Measurement of hardness The coating film formed in the above (i) was measured according to JIS K-540.
The pencil hardness was measured according to the 8.4.1 pencil scratch test of 0-1990. The surface hardness was evaluated by judging the scratches on the coating film.

The results are shown in Table 1. (vi) Evaluation of flattening property Instead of the SiO ₂ glass substrate used in (i) above,
A coating film was formed in the same manner as in the above (iii) except that a SiO ₂ wafer having a step of 1.0 μm was used. After that, the step difference of the substrate was measured using a stylus type film thickness measuring device.

The results are shown in Table 1. (vii) Adhesion test The substrate prepared in (i) above was subjected to a tape peeling test in accordance with JIS D-0202. When the amount of peeling was less than 2%, it was evaluated as ◯, when it was 2 to 5%, it was evaluated as Δ, and when it was more than 5%, it was evaluated as x.

The results are shown in Table 1. (viii) Storage stability The composition (1) was heated at 40 ° C. for 200 hours in a constant temperature incubator, and then the change in viscosity of the composition (1) was measured.

When the change in viscosity is less than 5%, it is designated as ◯, and 5 to
When it was 10%, it was evaluated as Δ, and when it exceeded 10%, it was evaluated as x. The results are shown in Table 1.

[0075]

[Example 2] A flask equipped with a dry ice / methanol reflux was replaced with nitrogen, and then 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved was charged. It is. Styrene 11.25g, methacrylic acid 3
3.75 g, dicyclopentanyl methacrylate 56.
25 g, glycidyl methacrylate 101.25 g and
After charging 22.5 g of 1,3-butadiene, gentle stirring was started. The temperature of the solution was raised to 80 ° C. and kept at this temperature for 5 hours.

Thereafter, the copolymer was prepared in the same manner as in Example 1.
I got (2). A thermosetting resin composition (2) was obtained in the same manner as in Example 1 except that the copolymer (1) was replaced with the copolymer (2).

The thermosetting resin composition (2) thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0078]

Example 3 A flask equipped with a dry ice / methanol reflux was purged with nitrogen and then charged with 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2′-azobisisobutyronitrile was dissolved. Successively, 12.37 g of styrene, 49.5 g of methacrylic acid, 56.25 g of dicyclopentanyl methacrylate, 90.0 g of glycidyl methacrylate and 16.8 of 1,3-butadiene.
After charging 8 g, gentle stirring was started. The temperature of the solution was raised to 80 ° C. and kept at this temperature for 5 hours.

Thereafter, the copolymer was prepared in the same manner as in Example 1.
I got (3). A thermosetting resin composition (3) was obtained in the same manner as in Example 1 except that the copolymer (1) was replaced with the copolymer (3).

The thermosetting resin composition (3) thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0081]

[Example 4] A flask equipped with a dry ice / methanol reflux was replaced with nitrogen, and then 459.0 g of a methyl 3-methoxypropionate solution in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved was charged. It is. Styrene 2
After charging 2.5 g, maleic anhydride 45.0 g, dicyclopentanyl methacrylate 67.5 g, glycidyl methacrylate 67.5 g and 1,3-butadiene 22.5 g, gentle stirring was started. The temperature of the solution was raised to 80 ° C. and kept at this temperature for 5 hours.

Thereafter, the copolymer was prepared in the same manner as in Example 1.
I got (4). A thermosetting resin composition (4) was obtained in the same manner as in Example 1 except that the copolymer (1) was replaced with the copolymer (4).

The thermosetting resin composition (4) thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0084]

Example 5 A flask equipped with a dry ice / methanol reflux was purged with nitrogen, and then 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2′-azobisisobutyronitrile was dissolved was charged. Continue p-
Methoxystyrene 22.5g, methacrylic acid 45.0
g, 2-methylcyclohexyl acrylate 56.25
g, 90.0 g of methacrylic acid-6,7-epoxyheptyl and 11.25 g of 1,3-butadiene were charged, and then gentle stirring was started. The temperature of the solution was raised to 80 ° C. and kept at this temperature for 5 hours.

Thereafter, the copolymer was prepared in the same manner as in Example 1.
I got (5). A thermosetting resin composition (5) was obtained in the same manner as in Example 1 except that the copolymer (1) was replaced with the copolymer (5).

The thermosetting resin composition (5) thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0087]

Example 6 The flask was purged with nitrogen, and then 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved was charged. Styrene 22.50g, methacrylic acid 4
4.50 g, dicyclopentanyl methacrylate 56.
After charging 25 g and 90 g of glycidyl methacrylate, gentle stirring was started. The temperature of the solution was raised to 80 ° C. and kept at this temperature for 5 hours.

Thereafter, the copolymer was prepared in the same manner as in Example 1.
I got (6). A thermosetting resin composition (6) was obtained in the same manner as in Example 1 except that the copolymer (1) was replaced with the copolymer (6).

The thermosetting resin composition (6) thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0090]

Example 7 The flask was purged with nitrogen, and then 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2′-azobisisobutyronitrile was dissolved was charged. Subsequently, 44.5 g of methacrylic acid, 90.0 g of dicyclopentanyl methacrylate and 90.0 g of glycidyl methacrylate were charged, and then gently stirring was started. The temperature of the solution was raised to 80 ° C. and kept at this temperature for 5 hours.

Thereafter, the copolymer was prepared in the same manner as in Example 1.
I got (7). A thermosetting resin composition (7) was obtained in the same manner as in Example 1 except that the copolymer (1) was replaced with the copolymer (7).

The thermosetting resin composition (7) thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0093]

Example 8 The flask was purged with nitrogen, and then 459.0 g of a methyl 3-methoxypropionate solution in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved was charged. Subsequently, 22.5 g of styrene, 45.0 g of maleic anhydride, 67.5 g of dicyclopentanyl methacrylate and 90 g of glycidyl methacrylate were charged, and then gently stirring was started. The temperature of the solution was raised to 80 ° C. and kept at this temperature for 5 hours.

Thereafter, the copolymer was prepared in the same manner as in Example 1.
I got (8). A thermosetting resin composition (8) was obtained in the same manner as in Example 1 except that the copolymer (1) was replaced with the copolymer (8).

The thermosetting resin composition (8) thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0096]

Example 9 The flask was purged with nitrogen, and then 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2′-azobisisobutyronitrile was dissolved was charged. Subsequently, 22.50 g of p-methoxystyrene, 45.0 g of methacrylic acid, 67.50 g of 2-methylcyclohexyl acrylate and 90.0 g of -6,7-epoxyheptylglycidyl methacrylate were charged, and then gently stirring was started. The temperature of the solution was raised to 80 ° C. and kept at this temperature for 5 hours.

Thereafter, the copolymer was prepared in the same manner as in Example 1.
I got (9). A thermosetting resin composition (9) was obtained in the same manner as in Example 1 except that the copolymer (1) was replaced with the copolymer (9).

The thermosetting resin composition (9) thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0099]

[Table 1]

[0100]

Comparative Example 1 In place of the copolymer (1) used in Example 1, EA-7130-1 (cresol novolac type epoxy resin in which acrylate is carboxylated,
A composition was obtained in the same manner as in Example 1 except that 25.0 g of an epoxy equivalent of 655 and an acid value of 80.5 (manufactured by Shin-Nakamura Chemical Co., Ltd.) was used.

This composition was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0102]

[Comparative Example 2] In Example 1, instead of the copolymer (1), EA-6540 (carboxylated acrylate in phenol novolac type epoxy resin, acid value 80) (Shin-Nakamura Chemical Co., Ltd.) A composition was obtained in the same manner as in Example 1 except that 25.0 g of the product (manufactured by K.K.) was used.

The composition was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0104]

Comparative Example 3 In Example 1, instead of the copolymer (1), EA-1040 (bisphenol A type epoxy resin obtained by carboxylating acrylate, acid value 8)
0) (manufactured by Shin-Nakamura Chemical Co., Ltd.) was used in the same manner as in Example 1 except that 25.0 g was used to obtain a composition.

This composition was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0106]

[Comparative Example 4] 25.0 g of ECN-1230 (cresol novolac type epoxy resin Araldite) (manufactured by Ciba Geigy) in place of the copolymer (1) in Example 1
And a curing agent DICY (dicyandiamide) 2.5 g were used to obtain a composition in the same manner as in Example 1.

This composition was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0108]

Comparative Example 5 In place of the copolymer (1) in Example 1, ECN-1237 (cresol novolac type epoxy resin araldite) (manufactured by Ciba Geigy) 25.0 g
And curing agent 2E4MZ (manufactured by Shikoku Chemicals Co., Ltd.) 2.5
A composition was obtained in the same manner as in Example 1 except that g was used.

This composition was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0110]

[Table 2]

[0111]

The thermosetting resin composition according to the present invention is excellent in storage stability and workability, and also has heat resistance, mechanical properties, chemical resistance, adhesiveness, transparency, smoothness and flatness. An excellent cured film can be easily formed.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuo Bessho 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] 1. An [A-1] (a-1) unsaturated carboxylic acid and / or
Alternatively, a copolymer of an unsaturated carboxylic acid anhydride, (a-2) an epoxy group-containing radically polymerizable compound, and (a-3) a monoolefinic unsaturated compound is dissolved in [B] an organic solvent. A thermosetting resin composition comprising: 2. An [A-2] (a-1) unsaturated carboxylic acid and / or
Or unsaturated carboxylic acid anhydride, (a-2) epoxy group-containing radically polymerizable compound, (a-3) monoolefin unsaturated compound, and (a-4) conjugated diolefin unsaturated compound A thermosetting resin composition, characterized in that the copolymer is dissolved in an organic solvent (B).