JP3321858B2 - Thermosetting resin composition - Google Patents

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 particularly, to a thermosetting resin composition which 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, workability, optical properties, smoothness, and flatness, and an epoxy-based thermosetting resin composition for a semiconductor.

[0002]

2. Description of the Related Art Conventionally, a thermosetting resin composition based on an epoxy resin has a resin obtained after curing having heat resistance,
Excellent in mechanical properties, chemical resistance, adhesiveness, workability and optical properties, so paints, electrical insulating materials, printed wiring boards, adhesives, civil engineering construction, jigs, molding materials, resin materials for sealing Widely used for such purposes.

[0003] This epoxy resin does not easily cause a sufficient curing reaction by itself. Conventionally, a cured film is formed from an epoxy resin by adding a special curing agent to the epoxy resin or curing the epoxy resin. Is modified with another resin or a carboxylic acid to cure the epoxy resin itself.

[0004]

However, the above-described conventional epoxy resins have various problems.

That is, when the epoxy resin is cured using a special curing agent, the compatibility between the epoxy resin and the curing agent, the storage stability, and the workability are 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 amount of modification at the time of modification, the modification reaction is complicated, and the quantitativeness of the reaction (unreacted reaction to the product) Effects of products and by-products)
Quality control. In addition, when a modified epoxy resin is produced, there is also a problem that an epoxy group and a carboxylic acid group react with each other and crosslink to gel the polymerization system.

Further, it has been difficult to flatten a substrate (hereinafter referred to as a "base substrate") using a conventional epoxy resin. For this reason, when a flat coating film is generally formed using epoxy resin, the substrate surface is first flattened to some extent with a low-viscosity, high-concentration material, and then the epoxy resin is applied, so that the substrate is coated. A flattened cured film was obtained. However, if a flattened cured film is to be obtained by such a method, the operation is complicated and the cost of the obtained cured film increases.

For this reason, the epoxy resin has excellent properties inherent to epoxy resin, excellent storage stability and excellent workability, and furthermore, glossiness, flatness of the underlying substrate, and the surface of the coating film itself. The emergence of an epoxy-based thermosetting resin composition that can easily obtain a cured film having excellent smoothness has been desired.

[0009]

Means for Solving the Problems The first thermosetting resin composition according to the present invention comprises: [A-1] (a-1) 30% by weight or less (excluding 0% by weight)
(A-2) 20 to 50% by weight of an epoxy group-containing radically polymerizable compound, and (a-3) 20 to 50% by weight of a monoolefin-based unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride. Copolymer with unsaturated compound, monoolefin unsaturated compound
A copolymer having a structural unit derived from (a-3) represented by the following general formula (4) or (5) is dissolved in an organic solvent [B].

Embedded image

Embedded image ( Where, in the formula (4), R ¹ is a hydrogen atom or a lower alkyl
And in formula (5), R ¹ is a hydrogen atom or lower
R ² is an alkyl group having 1 to 6 carbon atoms.
Or a cycloalkyl group having 5 to 12 carbon atoms.
The chloroalkyl group may have a substituent. )

[0010] The second thermosetting resin composition according to the present invention comprises: [A-2] (a-1) 30% by weight or less (excluding 0% by weight)
(A-2) 20 to 50% by weight of an epoxy group-containing radically polymerizable compound, and (a-3) 20 to 50% by weight of a monoolefin-based unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride. A copolymer of an unsaturated compound and (a-4) 5 to 15% by weight of a conjugated diolefin-based unsaturated compound;
The structural unit derived from the product (a-3) has the following general formula (4) or
The copolymer represented by the following general formula (5) is characterized by being dissolved in [B] an organic solvent.

Embedded image

Embedded image ( Where, in the formula (4), R ¹ is a hydrogen atom or a lower alkyl
And in formula (5), R ¹ is a hydrogen atom or lower
R ² is an alkyl group having 1 to 6 carbon atoms.
Or a cycloalkyl group having 5 to 12 carbon atoms.
The chloroalkyl group may have a substituent. )

The thermosetting resin composition according to the present invention contains a copolymer having both an epoxy group and a carboxylic acid group, and can be 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. A cured film excellent in flatness of the substrate and smoothness of the coating film itself can be easily obtained.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the thermosetting resin composition according to the present invention will be described. The copolymer used in the present invention comprises: (a-1) 30% by weight or less (not including 0% by weight) of an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride; (A-3) a copolymer of a radical polymerizable compound having an epoxy group of 50% by weight and a monoolefinically unsaturated compound of 20 to 50% by weight, wherein the monoolefinically unsaturated compound is
or (a-3) derived from a structural unit is represented by the following general formula (4) or the following general formula (5) is a copolymer [A-1], (a -1) 30 % by weight or less (0 (A-2 ) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride; (a-2) a radical polymerizable compound having 20 to 50% by weight of an epoxy group; and (a-3) 20 to 50. % by weight of monoolefinically unsaturated compounds, (a-4) a copolymer of 5 to 15 wt% conjugated diolefin unsaturated compound, the mono olefinically unsaturated compound
The structural unit derived from (a-3) is represented by the following general formula (4) or
It is a copolymer [A-2] represented by the general formula (5) .

Embedded image

Embedded image ( Where, in the formula (4), R ¹ is a hydrogen atom or a lower alkyl
A group, also in formula (5), R ¹ is a hydrogen atom or a lower
R ² is an alkyl group having 1 to 6 carbon atoms.
Or a cycloalkyl group having 5 to 12 carbon atoms.
The chloroalkyl group may have a substituent. )

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

Among them, acrylic acid, methacrylic acid and maleic anhydride are preferably used. Examples of the radical polymerizable compound having an epoxy group (a-2), for example, glycidyl acrylate, glycidyl methacrylate,
Glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, methacrylic acid-3,
4-epoxybutyl, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethylacrylate, and the like.

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

The monoolefinically unsaturated compound (a-3) includes, for example, alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate, methyl acrylate and isopropyl methacrylate. Alkyl acrylates such as acrylates, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate and other methacrylic acid cyclic alkyl esters, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl Acrylic acid cyclic alkyl esters such as acrylate, dicyclopentaoxyethyl acrylate, and isobornyl acrylate Phenyl methacrylate, methacrylic acid aryl esters such as benzyl methacrylate, phenyl acrylate, acrylic acid aryl esters such as benzyl acrylate, diethyl maleate, diethyl fumarate, a dicarboxylic acid diester of itaconic acid diethyl, styrene, alpha-methyl styrene,
m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate and the like.

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

The 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] comprising the constitutional unit derived from each component as described above includes the following formulas (1) to (5)
A copolymer comprising a structural unit represented by Further, as the copolymer [A-2], a copolymer composed of structural units represented by the following formulas (1) to (6) is preferable.
(1), (3), (4), (5), (6) a copolymer composed of structural units represented by the formula (2), (3), (4), (5), (6) )) Is preferable.

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

[0021]

Embedded image

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

[0023]

Embedded image

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

[0025]

Embedded image

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

[0027]

Embedded image

(Wherein 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 the cycloalkyl group is May be included.)

[0029]

Embedded image

(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 contains the above unsaturated carboxylic acid and It contains structural units derived from unsaturated carboxylic acid anhydrides (a-1) in an amount of preferably not more than 40% by weight, particularly preferably not more than 30% by weight.

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

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

When a copolymer is produced from only an unsaturated carboxylic acid or an unsaturated carboxylic anhydride (a-1) and an epoxy group-containing radically polymerizable compound (a-2), an epoxy group and a carboxylic acid There is a case where the polymerization reacts with an acid group and crosslinks to gel 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 an unsaturated carboxylic anhydride (a-1) and an epoxy group. In addition to the radically polymerizable compound (a-2), the monoolefinically unsaturated compound (a-3) and the conjugated diolefinically unsaturated compound (a-4) are copolymerized in the amounts described above, The epoxy group and the carboxylic acid group react with each other, so that the polymerization system is hardly gelled, and has excellent storage stability.

A copolymer having such a composition [A-1]
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 of the copolymer [A-1] or [A-2] is less than 10% by weight or a monoolefinically unsaturated compound (a-3). ) Structural unit is 7
When the content exceeds 0% by weight, the heat resistance of a cured film obtained from the thermosetting resin composition containing the copolymer [A-1] or [A-2] may be reduced.

The 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 steps of 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 the copolymer [A-1] or [A-2] may be reduced.

The copolymers [A-1] and [A-
2] is soluble in an aqueous alkaline solution. The copolymers [A-1] and [A-2] as described above can be produced by a copolymerization step alone without a 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 an epoxy group, (a-3) monoolefinic unsaturated compound and / or (a-4) conjugate The diolefin-based unsaturated compound can be obtained by radical polymerization in a solvent in the presence of a catalyst (polymerization initiator).

Examples of the solvent used here include alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, cellosolve esters such as methyl cellosolve acetate, aromatic hydrocarbons, and the like.
Examples 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 dimethylvaleronitrile) and 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1'-bis- (T-
Organic peroxides such as butylperoxy) cyclohexane and hydrogen peroxide.

When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator. The copolymer [A-
The molecular weight of [1] or [A-2] and the distribution thereof are as long as the solution of the composition of the present invention can be uniformly applied.
There is no particular limitation.

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

The thermosetting resin composition according to the present invention comprises:
The copolymer [A-1] and the copolymer [A-2] may be used in combination. As the organic solvent used in the present invention, those that can uniformly dissolve the copolymer [A-1] or [A-2] and do not react with them 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, ethyl cellosolve acetate and the like. Of ethylene glycol alkyl ether acetates, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, and fragrances such as toluene and xylene 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.

Further, together with these, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, 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, High boiling solvents 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 preferred in view of solubility, reactivity with each component, and the like. Esters such as ethyl and diethylene glycols such as diethylene glycol monomethyl ether are preferably used.

These are used alone or in combination. In the thermosetting resin composition according to the present invention,
[B] The organic solvent is the above-mentioned 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. Further, the thermosetting resin composition has excellent storage stability and excellent workability.

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

The thermosetting resin composition according to the present invention may contain components other than those described above, if necessary, as long as the object of the present invention is not impaired.

As such other components, a surfactant is 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, S-113, S-131, S-141, S-145 (manufactured by Asahi Glass Co., Ltd.), SH-28PA,
190, -193, SZ-6032, SF-8428
A commercially available fluorine-based surfactant 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.

An adhesion aid may be used to improve the adhesion to the substrate. As the adhesion assistant, 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, or 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 aids can be used alone or in combination of two or more. The adhesion assistant is preferably 20 parts by weight or less, more preferably 0.05 to 1 part by weight, based on 100 parts by weight of the copolymers [A-1] and [A-2].
It is used in an amount of 0 parts by weight.

Formation of Coating Film (Curing Film) A desired coating film can be formed by applying the above-mentioned thermosetting resin composition to a substrate surface and removing the solvent by heating. The method of coating the substrate surface is not particularly limited, and various methods such as a spray method, a roll coating method, and a spin coating method can be employed.

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

[0058]

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

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

[0060]

Example 1 Synthesis of Copolymer After replacing a flask equipped with a dry ice / methanol reflux condenser 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 coagulate 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. After performing the re-dissolution-coagulation operation a total of three times, the obtained coagulated product was vacuum-dried at 40 ° C. for 48 hours to obtain a desired copolymer (1).

Preparation of Thermosetting Resin Composition After dissolving 25 g of the above copolymer (1) in 75 g of diethylene glycol dimethyl ether, the solution was filtered through a 0.22 μm Millipore filter and the thermosetting resin composition (1) was obtained.
Was prepared.

(I) Formation of Coating Film The above composition (1) was applied on a SiO ₂ glass substrate using a spinner, and then heated at 180 ° C. for 30 minutes on a hot plate to form a film having a thickness of 2. A 0 μm coating 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 in (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 double beam (Hitachi, Ltd.)).
At this time, the case where the minimum transmittance exceeds 98% is defined as Δ, and 9
The case of 5 to 98% was rated as Δ, and the case of less than 95% was rated as x.

Table 1 shows the results. (iii) Evaluation of heat resistance Using the substrate on which the coating film was formed in (i) above,
Heating was performed for 1 hour on a hot plate at ℃, and the heat resistance was evaluated based on the rate of change in film thickness before and after heating (remaining film ratio).

The case where the remaining film ratio exceeds 98% is defined as Δ, and 9
The case of 5 to 98% was rated as Δ, and the case of less than 95% was rated as x. Table 1 shows the results.

(Iv) Evaluation of heat discoloration resistance Using the substrate on which the coating film was formed in (i) above,
The composition was heated on a hot plate at 1 ° C. for 1 hour, and the heat discoloration resistance was evaluated based on the change in transmittance. The case where the rate of change at this time is less than 5% is Δ, and the case where it is 5 to 10% is Δ,
The case where it exceeded 10% was evaluated as x.

The transmittance was determined in the same manner as in (ii) Evaluation of transparency.

Table 1 shows the results. (v) Measurement of hardness The coating film formed in (i) above was subjected to JIS K-540.
The pencil hardness was measured according to the 8.4.1 pencil scratch test of 0-1990. The evaluation was based on the scratches of the coating film, and the surface hardness was evaluated.

Table 1 shows the results. (vi) Flatness evaluation 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 an SiO ₂ wafer having a step of 1.0 μm was used. Thereafter, the step of the substrate was measured using a stylus-type film thickness measuring instrument.

Table 1 shows the results. (vii) Adhesion test The substrate prepared in the above (i) was subjected to a tape peeling test according to JIS D-0202. The case where the peeling was less than 2% was rated as Δ, the case where the peeling was 2 to 5% was rated as Δ, and the case where the peeling exceeded 5% was rated as ×.

Table 1 shows the results. (viii) After storage stability composition (1) was heated at 40 ° C. for 200 hours in a constant temperature thermostat, the change in viscosity of composition (1) was measured.

When the change in viscosity was less than 5%,
The case of 10% was evaluated as Δ, and the case of exceeding 10% was evaluated as x. Table 1 shows the results.

[0075]

Example 2 After a flask equipped with a dry ice / methanol reflux condenser was purged with nitrogen, 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. Subsequently, 11.25 g of styrene and 3 of methacrylic acid were added.
3.75 g, dicyclopentanyl methacrylate
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.
(2) was obtained. 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) was evaluated in the same manner as in Example 1. Table 1 shows the results.

[0078]

Example 3 After a flask equipped with a dry ice / methanol reflux condenser was purged with nitrogen, 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved was charged. Subsequently, 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 were used.
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.
(3) was obtained. 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 obtained thermosetting resin composition (3) was evaluated in the same manner as in Example 1. Table 1 shows the results.

[0081]

Example 4 After a flask equipped with a dry ice / methanol reflux condenser was purged with nitrogen, 459.0 g of a methyl 3-methoxypropionate solution in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved was charged. It is. Continue with styrene 2
After 2.5 g, 45.0 g of maleic anhydride, 67.5 g of dicyclopentanyl methacrylate, 67.5 g of glycidyl methacrylate, 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 copolymer was prepared in the same manner as in Example 1.
(4) was obtained. 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 obtained thermosetting resin composition (4) was evaluated in the same manner as in Example 1. Table 1 shows the results.

[0084]

Example 5 A flask equipped with a dry ice / methanol reflux condenser 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 22.5 g, methacrylic acid 45.0
g, 2-methylcyclohexyl acrylate 56.25
g, 90.0 g of 6,7-epoxyheptyl methacrylate and 11.25 g of 1,3-butadiene, and then stirring was started slowly. 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.
(5) was obtained. 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) was evaluated in the same manner as in Example 1. Table 1 shows the results.

[0087]

Example 6 After the flask was purged with nitrogen, 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved was charged. Successively, 22.50 g of styrene and 4 of methacrylic acid
4.50 g, dicyclopentanyl methacrylate
After 25 g and 90 g of glycidyl methacrylate were charged, 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.
(6) was obtained. 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 obtained thermosetting resin composition (6) was evaluated in the same manner as in Example 1. Table 1 shows the results.

[0090]

Example 7 After replacing the flask with nitrogen, 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved was charged. Subsequently, after 44.5 g of methacrylic acid, 90.0 g of dicyclopentanyl methacrylate, and 90.0 g of glycidyl methacrylate were charged, 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.
(7) was obtained. 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 obtained thermosetting resin composition (7) was evaluated in the same manner as in Example 1. Table 1 shows the results.

[0093]

Example 8 After replacing the flask with nitrogen, 459.0 g of a methyl 3-methoxypropionate solution in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved was charged. Subsequently, after 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, stirring was started slowly. 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.
(8) was obtained. 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 same evaluation as in Example 1 was performed on the obtained thermosetting resin composition (8). Table 1 shows the results.

[0096]

Example 9 After the atmosphere in the flask was replaced with nitrogen, 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 methacrylic acid-6,7-epoxyheptylglycidyl were charged, and then stirring was started gently. 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.
(9) was obtained. 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 same evaluation as in Example 1 was performed for the obtained thermosetting resin composition (9). Table 1 shows the results.

[0099]

[Table 1]

[0100]

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

This composition was evaluated in the same manner as in Example 1. Table 2 shows the results.

[0102]

Comparative Example 2 In Example 1, EA-6540 (carboxylated acrylate in phenol novolak type epoxy resin, acid value 80) was used instead of copolymer (1) (Shin Nakamura Chemical Co., Ltd.) Except that 25.0 g was used, a composition was obtained in the same manner as in Example 1.

This composition was evaluated in the same manner as in Example 1. Table 2 shows the results.

[0104]

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

This composition was evaluated in the same manner as in Example 1. Table 2 shows the results.

[0106]

Comparative Example 4 In Example 1, 25.0 g of ECN-1230 (cresol novolak type epoxy resin araldite) (manufactured by Ciba Geigy) was used in place of copolymer (1).
A composition was obtained in the same manner as in Example 1, except that 2.5 g of the curing agent DICY (dicyandiamide) was used.

This composition was evaluated in the same manner as in Example 1. Table 2 shows the results.

[0108]

Comparative Example 5 In Example 1, 25.0 g of ECN-1237 (cresol novolak type epoxy resin araldite) (manufactured by Ciba Geigy) was used in place of copolymer (1).
And curing agent 2E4MZ (manufactured by Shikoku Chemical Industry Co., Ltd.) 2.5
Except for using g, a composition was obtained in the same manner as in Example 1.

This composition was evaluated in the same manner as in Example 1. Table 2 shows the results.

[0110]

[Table 2]

[0111]

The thermosetting resin composition according to the present invention has excellent storage stability and workability, as well as heat resistance, mechanical properties, chemical resistance, adhesion, transparency, smoothness and flatness. It is possible to easily form a cured film excellent in quality.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Nobuo Bessho 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-2-180921 (JP, A) JP-A Heisei 2-300215 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 59/20-59/38 C08L 35/00 C08L 37/00

Claims (3)

(57) [Claims] [A-1] (a-1) 30% by weight or less (0% by weight)
Unsaturated carboxylic acids and / or unsaturated carboxylic acid anhydride the exclusive), and (a-2) 20 to 50 wt% of an epoxy group-containing radical polymerizable compound, (a-3) 20 to 50 wt% Is a copolymer with a monoolefinically unsaturated compound,
(B-3) a thermosetting resin characterized in that a copolymer having a structural unit derived from (a-3) represented by the following general formula (4) or (5) is dissolved in an organic solvent [B]: Resin composition: Embedded image ( Where, in the formula (4), R ¹ is a hydrogen atom or a lower alkyl
A group, also in formula (5), R ¹ is a hydrogen atom or a lower alkyl group
R ² is an alkyl group having 1 to 6 carbon atoms or 5 carbon atoms.
To 12 cycloalkyl groups,
The group may have a substituent. ). [A-2] (a-1) 30% by weight or less (0% by weight )
Unsaturated carboxylic acids and / or unsaturated carboxylic acid anhydride the exclusive), and (a-2) 20 to 50 wt% of an epoxy group-containing radical polymerizable compound, (a-3) 20 to 50 wt% A copolymer of (a-4) 5 to 15% by weight of a conjugated diolefinically unsaturated compound , wherein the monoolefinically unsaturated compound is
The structural unit derived from the product (a-3) has the following general formula (4) or
Following general formula (5) is a copolymer, [B] a thermosetting resin composition characterized by comprising dissolved in an organic solvent: ## STR3 ## Embedded image ( Where, in the formula (4), R ¹ is a hydrogen atom or a lower alkyl
A group, also in formula (5), R ¹ is a hydrogen atom or a lower alkyl group
R ² is an alkyl group having 1 to 6 carbon atoms or 5 carbon atoms.
To 12 cycloalkyl groups,
The group may have a substituent. ). 3. A cured film formed from the thermosetting resin composition according to claim 1.