JPH10207062A - Photosensitive resin composition - Google Patents

Abstract

(57) [Problem] To provide a photosensitive resin composition which does not cause coloring with time or thickening gelation, has excellent storage stability, and gives a cured product having excellent heat resistance. SOLUTION: (A) Structural unit (I) comprising styrene, vinyl ether compound or α-olefin, maleic anhydride unit (II) and (meth) acrylate unit (III), and their composition molar ratio is , [Structural unit (I) comprising styrene, vinyl ether compound or α-olefin]: [Maleic anhydride unit (I
I)]: [(meth) acrylate unit (III)]
= 1: 0.9-1.1: 0.2-1.5 and a glass transition temperature (Tg) of 90 ° C. or more was obtained by the following general formula (1). (Wherein R ¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ² represents an alkylene group having 1 to 3 carbon atoms). A) a photosensitive resin composition comprising a diluent and (C) a photopolymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition,
More specifically, the present invention relates to a resin composition which is cured by light.

[0002]

2. Description of the Related Art A photosensitive resin obtained by reacting a copolymer of a maleic anhydride with a vinyl ether compound such as styrene or methyl vinyl ether or an α-olefin such as isobutylene with a (meth) acrylic ester having a hydroxyl group. A photocurable resin composition comprising a polymerizable monomer, a diluent such as an organic solvent, and a photopolymerization initiator is known (see JP-A-49-37701), and is used for applications such as photoresist materials. Have been.

In the above resin composition, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and a reaction of (meth) acrylic acid with styrene oxide are used as (meth) acrylates having a hydroxyl group. Products, such as the reaction product of (meth) acrylic acid and butyl glycidyl ether,
These are difficult to obtain industrially or relatively expensive.

Further, the double bond in such a (meth) acrylic acid ester is generally liable to be thermally polymerized, so that the double bond in the (meth) acrylic acid ester is liable to be remarkably thickened or cross-linked to form a gel when reacting with the above-mentioned copolymer. was there.

Further, the photosensitive resin obtained by the reaction between the above copolymer and a (meth) acrylic acid ester having a hydroxyl group has insufficient storage stability, and is colored with time or thickened due to gelation. There was a tendency that it became.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have proposed a composition which can solve the above-mentioned problems, which comprises (a) styrene, vinyl ether compound or α-olefin with maleic anhydride and (meth) acrylate. 3 for the copolymer
A photosensitive resin composition comprising a photosensitive resin obtained by adding -methyl-3-buten-1-ol by an esterification reaction, (b) a diluent, and (c) a photopolymerization initiator. Has already filed a patent application (Japanese Unexamined Patent Publication No. Hei 5-345).
No. 815).

The above photosensitive resin composition has sufficient storage stability, and can easily adjust the properties of the base polymer. However, in recent years, a higher performance photosensitive resin composition has been required, and when used as a photoresist material as described above, it is required to exhibit excellent heat resistance after curing. I have. An object of the present invention is to provide a photosensitive resin composition that does not cause coloring over time or gelling with time and that gives a cured product excellent in heat resistance in order to meet such a demand.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that, in the photosensitive resin composition described in JP-A-5-345815, the glass transition point of the base polymer is increased to increase the glass transition point. The present inventors have found that the above-mentioned problem can be solved, and as a result of further study, have completed the present invention. That is, the present invention relates to (A) a structural unit (I) composed of styrene, a vinyl ether compound or an α-olefin, a maleic anhydride unit (II) and (meth)
It is composed of acrylic ester units (III), and their composition molar ratio is [structural unit (I) composed of styrene, vinyl ether compound or α-olefin]: [maleic anhydride unit (II)]: [(meth) acrylic Acid ester unit (III)] = 1: 0.9 to 1.1: 0.2 to 1.5, and a copolymer having a glass transition temperature (Tg) of 90 ° C. or higher is represented by the following general formula: (1)

[0009]

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(Wherein, R ¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ² represents an alkylene group having 1 to 3 carbon atoms). , (B) a diluent, and (C) a photopolymerization initiator.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive resin (A) used in the present invention is styrene, a vinyl ether compound or α.
-An olefinic structural unit (I) [hereinafter sometimes abbreviated as a structural unit (I)], a maleic anhydride unit (II) and a (meth) acrylic ester unit (II)
It is a resin obtained by esterifying a copolymer comprising I) (hereinafter abbreviated as a maleic anhydride copolymer) with an unsaturated alcohol represented by the general formula (1).

The structural unit (I) constituting the maleic anhydride copolymer includes, for example, styrene; vinyl ether compounds such as methyl vinyl ether, ethylene, propylene, 1-butene, isobutylene, 1-pentene and 1-pentene.
Structural units derived from α-olefins having 2 to 8 carbon atoms having a double bond at the terminal such as hexene, 1-heptene and 1-octene are exemplified, and among these, isobutylene units are preferable.

The (meth) acrylate unit (III) constituting the maleic anhydride copolymer includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and butyl (meth) acrylate. ) Acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth)
Examples include structural units derived from various (meth) acrylic esters such as acrylates, and are appropriately selected in consideration of the polymer physical properties required for the photosensitive resin (A). In this specification, “(meth) acrylate” is a general term for acrylate and methacrylate, and “(meth) acrylate” is a general term for acrylate and methacrylate.

The above maleic anhydride copolymer is prepared from a vinyl ether compound such as styrene or vinyl ether or an α-olefin such as isobutylene and maleic anhydride and a (meth) acrylic acid ester (hereinafter, these are referred to as raw material monomers). , According to a conventional method. For example, it can be produced by charging a raw material monomer in a reaction vessel and copolymerizing it with a radical polymerization initiator in a solvent by a solution polymerization method or the like.

As the radical polymerization initiator, those conventionally used can be used without particular limitation.
For example, di (dodecanoyl) peroxide, benzoyl peroxide, cumene hydroperoxide, t
Organic peroxides such as -butyl hydroperoxide;
2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,
2'-azobisisobutyrate, α, α'-azo-α-
An azo compound such as ethylbutyronitrile can be used.

Examples of the solvent used in the solution polymerization include various solvents that do not inhibit radical polymerization, for example, ketones such as acetone and methyl ethyl ketone;
Aliphatic hydrocarbons such as hexane and n-octane; aromatic hydrocarbons such as benzene, toluene and ethylbenzene;
Esters such as ethyl acetate and isopropyl acetate; ethers such as diisopropyl ether, dioxane and tetrahydrofuran; chlorinated hydrocarbons such as methylene chloride and chloroform can be used. These solvents may be used alone or as a mixture of two or more. The polymerization temperature is usually 0 to 200 ° C, preferably 30 to 150 ° C, and the polymerization time is usually 1 to 50 hours,
Preferably, it is 2 to 20 hours.

After completion of the polymerization, the formed maleic anhydride copolymer is separated and recovered by filtering and removing the precipitated polymer by filtration or by removing the solvent from the polymer solution, and then removing the remaining polymer. It is performed by drying.

The above maleic anhydride copolymer has various properties by changing the composition molar ratio of the structural unit (I), maleic anhydride unit (II) and (meth) acrylate unit (III). However, if the molar ratio of the (meth) acrylate unit (III) is too small, the solubility in the diluent (B) described below decreases, making it difficult to use the photosensitive resin composition as a solution. In addition to the above, the film-forming property is reduced when the composition is applied to a flat plate or the like. On the other hand, if the molar ratio of the (meth) acrylate unit (III) is too large, the degree of easiness of removal of the unexposed portion of the maleic anhydride copolymer by dissolution and removal with an aqueous alkali solution, that is, alkali developability, descend.

The composition molar ratio of each structural unit in the maleic anhydride copolymer is as follows: [structural unit (I)]: [maleic anhydride unit (II)]: [(meth) acrylate unit (III)] = 1: 0.9 to 1.1: 0.2 to 1.5, [Structural unit (I)]: [Maleic anhydride unit (II)]: [(meth) acrylic ester (Unit (III)) = 1: 0.9 to 1.1: 0.5 to 1.2.

The maleic anhydride copolymer needs to have a glass transition temperature (Tg) of 90 ° C. or higher in order to obtain a photosensitive resin composition which gives a cured product having sufficient heat resistance. The glass transition temperature of the maleic anhydride copolymer is preferably 110 ° C. or higher. The glass transition temperature of the maleic anhydride copolymer can be set within the above range by appropriately selecting the type and composition of the raw material monomers.

The preferred range of the weight-average molecular weight (Mw) of the maleic anhydride copolymer varies depending on the use as a photosensitive resin composition.
It is.

In the general formula (1) representing an unsaturated alcohol used for esterification of a maleic anhydride copolymer,
The alkylene group having 1 to 3 carbon atoms represented by ² is, specifically,
Examples include a methylene group, an ethylene group, a propylene group, and a trimethylene group. Here, specific examples of the unsaturated alcohol represented by the general formula (1) include 2-propen-1-ol, 3-buten-1-ol, 3-methyl-3-buten-1-ol, -Methyl-3-buten-1-ol,
Examples thereof include 4-penten-1-ol and 4-methyl-4-penten-1-ol, among which 3-buten-1-ol and 3-methyl-3-buten-1-ol are preferable. .

The unsaturated alcohol represented by the general formula (1) reacts with the acid anhydride group of the maleic anhydride copolymer to form an ester to be added to the copolymer. Here, the addition amount of the unsaturated alcohol is x (mol) of the number of moles of the unsaturated alcohol added to the maleic anhydride copolymer, and the acid anhydride in the maleic anhydride copolymer before the addition of the unsaturated alcohol. When the number of moles of the group is y (mol), the molar ratio (x / y) of the two is preferably 0.5 or more, more preferably 1 or more, and 1.5 or more. More preferred. The upper limit of the amount of the unsaturated alcohol added does not exceed 2 in the above molar ratio (x / y).

The esterification of the maleic anhydride copolymer with the unsaturated alcohol represented by the general formula (1) can be carried out according to a conventional method, and the esterification of the unsaturated alcohol represented by the general formula (1) with the maleic anhydride is carried out. A simple and preferred method is to heat the polymer in the presence of an esterification catalyst and, if desired, an organic solvent or a polymerization inhibitor such as hydroquinone.

Examples of the esterification catalyst include an acid catalyst such as formic acid and p-toluenesulfonic acid; and a basic catalyst such as a tertiary amine, pyridine and imidazole compounds. The amount of the esterification catalyst used is preferably 0.1 to 5% by weight based on the maleic anhydride copolymer. As the solvent, a solvent that dissolves both the raw material and the product, such as acetone, dimethylformamide, and tetrahydrofuran, is preferably used.

The reaction temperature of the esterification depends on the amount of the catalyst used,
Although it depends on the composition and molecular weight of the maleic anhydride copolymer, it is usually 50 to 200 ° C., and the reaction time is usually 1 to 40 hours.

After completion of the reaction, the unreacted unsaturated alcohol and the solvent used are removed to obtain the photosensitive resin (A).

The photosensitive resin (A) thus obtained is obtained when all of the acid anhydride groups in the original maleic anhydride copolymer have been converted to diesters, that is, the above molar ratio (x / y). Except when (2) is 2, the compound has a carboxyl group or an acid anhydride group in the molecule, and is soluble in an aqueous alkali solution such as an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and aqueous ammonia.

The diluent (B) in the present invention can dissolve the above-mentioned photosensitive resin (A), and examples thereof include a photopolymerizable monomer, an organic solvent, and an aqueous alkali solution. The diluent (B) may be used alone or in combination of two or more.

Here, as the photopolymerizable monomer, a monomer having radical polymerizability can be used.
Trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-hydroxyethyl (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, N-vinylpyrrolidone , Cyclohexyl acrylate, phenoxyethyl acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, and the like.

Examples of the organic solvent include aromatic hydrocarbons such as benzene and toluene; acetates such as ethyl acetate, butyl acetate, methyl cellosolve acetate and carbitol acetate; ethyl cellosolve;
Cellosolves such as butyl cellosolve; petroleum solvents such as petroleum ether;

Further, examples of the aqueous alkali solution include an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and aqueous ammonia. The amount of the diluent (B) used is not particularly limited, but is usually in the range of 0.25 to 20 times, preferably 1 to 9 times the weight of the photosensitive resin (A).

The photopolymerization initiator (C) used in the present invention
Is a compound that generates a radical upon irradiation with light, and examples thereof include benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; benzophenone, chloroacetophenone, 2,2-diethoxyacetophenone, and 2-hydroxy- Aromatic ketones such as 2-methylpropiophenone; thioxanthones such as 2-chlorothioxanthone and 2,4-diethylthioxanthone; anthraquinones such as chloroanthraquinone and ethylanthraquinone;
Ketals such as acetophenone dimethyl ketal; and other benzoylphosphine oxides and Michler's ketone. The photopolymerization initiator (C) may be used alone or in combination of two or more. The use amount of the photopolymerization initiator (C) is not particularly limited, but is usually in the range of 0.5 to 10% by weight based on the photosensitive resin (A).

Incidentally, a polymerization inhibitor such as hydroquinone and methylhydroquinone can be added to the photosensitive resin composition of the present invention. In addition, for the purpose of coating properties, adjustment of coating film hardness and adhesion, coloring, etc., inorganic fillers such as barium sulfate, talc, clay, calcium carbonate, glass powder, dyes and pigments such as phthalocyanine blue and phthalocyanine green, and silicon. An antifoaming agent such as a fluorine-based or fluorine-based agent, a leveling agent, and the like can be used in combination as needed.

The photosensitive resin composition of the present invention is obtained by appropriately removing an organic solvent, water and the like contained in the composition,
Curing can be performed by irradiating active light rays (ultraviolet rays) such as a metal halide lamp, a xenon lamp, a carbon arc lamp, and sunlight. Further, the photosensitive resin composition of the present invention can be cured by irradiating radiation such as electron beam, laser beam, X-ray, and gamma ray.

The photosensitive resin composition of the present invention can be used as an image forming material such as relief printing, stamps, seals, name plates, decorative molds, etching photoresists, printed circuit boards, etc. Utilizing heat resistance, it is particularly effectively used in applications such as printed circuit boards.

[0037]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 (a) Synthesis of photosensitive resin Acetone was placed in an autoclave having an internal volume of 1 liter.
After charging 7 g and replacing the inside of the container with nitrogen, 27.5 g of isobutylene was charged and the temperature was raised to 100 ° C. Subsequently, 2,2′-azobis (2-methylbutyronitrile) 5.
A mixed solution of 9 g, 40 g of maleic anhydride, 23.2 g of n-butyl methacrylate, and 132.9 g of acetone was continuously charged over a period of 6 hours, and a polymerization reaction was carried out at 100 ° C. over a further 7 hours, a total of 7 hours. After the polymerization, remove the reaction solution from the autoclave and air-dry overnight,
Vacuum drying was performed at 80 ° C. to obtain 84.3 g of maleic anhydride copolymer 1.

The physical properties of the maleic anhydride copolymer 1 were as follows. Composition molar ratio (by ¹ H-NMR analysis) Isobutylene unit: Maleic anhydride unit: n-butyl methacrylate unit = 1: 1: 0.4 Average molecular weight [GPC measurement (in terms of polystyrene)] Mn = 6500, Mw = 11100 Glass transition temperature (by DSC measurement) 115 ° C

Next, 50 g of the obtained maleic anhydride copolymer 1 and 3-methyl-3-buten-1-ol 300
g, 5 g of pyridine and 0.02 g of hydroquinone were charged into an autoclave having an internal volume of 1 liter, the atmosphere in the vessel was replaced with nitrogen, and the mixture was heated at 130 ° C. for 5 hours to carry out an esterification reaction. Using an evaporator and a vacuum dryer,
Unreacted 3-methyl-3-buten-1-ol and pyridine were removed to obtain 61.9 g of photosensitive resin 1.

From the results of the IR spectrum and the measurement of the acid value, it was found that the photosensitive resin 1 obtained as described above shows that 3-methyl-3-butene-1-mol per mole of the acid anhydride group in the maleic anhydride copolymer 1 was used. It turned out to be an esterified product obtained by adding 1.9 mol of all.

(B) Preparation of photosensitive resin composition: 20 g of the photosensitive resin 1 obtained above, 10 g of trimethylolpropane triacrylate and 0.4 g of benzophenone were dissolved in 30 g of carbitol acetate, and the photosensitive resin composition was dissolved. 1 was prepared. The photosensitive resin composition 1 comprises:
After standing at room temperature for one month in a dark place, no coloring, thickening with time, gelation, etc. were observed.

The photosensitive resin composition 1 obtained above was applied on an aluminum plate using an applicator and dried to obtain a coating film having a thickness of 40 μm. The coating film was irradiated with ultraviolet rays (2 kW mercury lamp) from a distance of 30 cm for 60 seconds. After the end of the ultraviolet irradiation, the film was immersed in acetone to confirm that the unexposed portion of the coating film was dissolved, and that the exposed portion of the coating film was cured and did not dissolve. It was immersed in a 5% aqueous solution of sodium hydroxide at 40 ° C., and it was confirmed that the unexposed portion of the coating film was dissolved and that the exposed portion of the coating film was cured and did not dissolve. 260 on the exposed part (cured part)
When the soldering iron adjusted to ° C. was applied for 5 seconds, it was confirmed that the cured coating film did not swell or peel off and showed sufficient heat resistance.

Example 2 (a) Synthesis of photosensitive resin Toluene 200 was placed in an autoclave having an inner volume of 1 liter.
g, 49.1 g of maleic anhydride, 60.1 g of methyl methacrylate, and 1.5 g of 2,2′-azobisisobutyronitrile, and after the inside of the vessel was replaced with nitrogen, 82 g of isobutylene was charged and the temperature was increased. The polymerization reaction was performed at 70 ° C. for 8 hours. After completion of the polymerization, the reaction mixture was taken out of the autoclave, and the precipitate was filtered and air-dried overnight.
Vacuum drying was performed at 0 ° C. to obtain 133.1 g of maleic anhydride copolymer 2.

The physical properties of the maleic anhydride copolymer 2 were as follows. Composition molar ratio (by ¹ H-NMR analysis) Isobutylene unit: Maleic anhydride unit: Methyl methacrylate unit = 1: 1: 1.16 Average molecular weight [by GPC measurement (in terms of polystyrene)] Mn = 23200, Mw = 63400 Glass transition Temperature (by DSC measurement) 125 ° C

Next, 50 g of the obtained maleic anhydride copolymer 2, 300 g of 3-buten-1-ol, pyridine 5
g and 0.02 g of hydroquinone were charged into an autoclave having an internal volume of 1 liter, the atmosphere in the vessel was replaced with nitrogen, and the mixture was heated at 110 ° C. for 10 hours to carry out an esterification reaction. Using an evaporator and a vacuum dryer, unreacted 3
-Buten-1-ol and pyridine were removed to obtain 63.8 g of photosensitive resin 2. From the measurement results of the IR spectrum and the acid value, the photosensitive resin 2 obtained above had 1.92 mol of 3-buten-1-ol added per mol of the acid anhydride group in the maleic anhydride copolymer 2. It was found to be an esterified product.

(B) Preparation of photosensitive resin composition 20 g of the photosensitive resin 2 obtained above, 10 g of trimethylolpropane triacrylate and 0.4 g of benzophenone were dissolved in 30 g of carbitol acetate, and the photosensitive resin composition was dissolved. 2 was prepared. The photosensitive resin composition 2 comprises:
After standing at room temperature for one month in a dark place, no coloring, thickening with time, gelation, etc. were observed.

The photosensitive resin composition 2 obtained above was applied on an aluminum plate using an applicator and dried to obtain a coating having a thickness of 40 μm. The coating film was irradiated with ultraviolet rays (2 kW mercury lamp) from a distance of 30 cm for 60 seconds. After the end of the ultraviolet irradiation, the film was immersed in acetone to confirm that the unexposed portion of the coating film was dissolved, and that the exposed portion of the coating film was cured and did not dissolve. Further, it was immersed in a 5% aqueous solution of sodium hydroxide at 40 ° C., and it was confirmed that the unexposed portion of the coating film was dissolved, and that the exposed portion of the coating film was cured and did not dissolve. 26 in the exposed part (cured part)
When the soldering iron adjusted to 0 ° C. was applied for 5 seconds, it was confirmed that the cured coating film did not swell or peel off and showed sufficient heat resistance.

Comparative Example 1 (a) Synthesis of photosensitive resin Acetone 127. was placed in an autoclave having an inner volume of 1 liter.
9 g, 14.7 g of maleic anhydride and 17.9 g of n-butyl acrylate were charged, the atmosphere in the vessel was replaced with nitrogen, and then 30.9 g of isobutylene was charged and the temperature was raised. Subsequently, 2,2'-azobisisobutyronitrile 1.
A mixed solution of 15 g, 34.3 g of maleic anhydride, 7.7 g of n-butyl acrylate, and 60 g of acetone was continuously charged over 5 hours, and the polymerization reaction was further performed at 70 ° C. for 8 hours at 3 hours for a total of 8 hours. Was. After the polymerization, remove the reaction solution from the autoclave and air-dry overnight,
Vacuum drying was performed at 80 ° C. to obtain 98.7 g of maleic anhydride copolymer 3.

The physical properties of the maleic anhydride copolymer 3 were as follows. Composition molar ratio (by ¹ H-NMR analysis) Isobutylene unit: maleic anhydride unit: n-butyl acrylate unit = 1: 1: 0.39 Average molecular weight [determined by GPC (in terms of polystyrene)] Mn = 36100, Mw = 96300 Glass transition temperature (according to DSC measurement) 70.5 ° C

Next, 50 g of the obtained maleic anhydride copolymer 3 and 3-methyl-3-buten-1-ol 300
g, 5 g of pyridine and 0.02 g of hydroquinone were charged into an autoclave having an internal volume of 1 liter. After the atmosphere in the vessel was replaced with nitrogen, the mixture was heated at 110 ° C. for 10 hours to carry out an esterification reaction. Unreacted 3-methyl-3-buten-1-ol and pyridine were removed using an evaporator and a vacuum dryer, and 70.2 g of photosensitive resin 3 was obtained.
From the measurement results of the IR spectrum and the acid value, it was found that the photosensitive resin 3 obtained above contained 1-methyl-3-buten-1-ol per mole of the acid anhydride group in the maleic anhydride copolymer 3. It was found to be an esterified product obtained by adding 0.9 mol.

(B) Preparation of Photosensitive Resin Composition 20 g of the photosensitive resin 3 obtained above, 10 g of trimethylolpropane triacrylate and 0.4 g of benzophenone were dissolved in 30 g of carbitol acetate to obtain a photosensitive resin composition. 3 was prepared. The photosensitive resin composition 3 comprises:
After standing at room temperature for one month in a dark place, no coloring, thickening with time, gelation, etc. were observed.

The photosensitive resin composition 3 obtained above was applied on an aluminum plate using an applicator and dried to obtain a coating film having a thickness of 40 μm. The coating film was irradiated with ultraviolet rays (2 kW mercury lamp) from a distance of 30 cm for 60 seconds. After the end of the ultraviolet irradiation, the film was immersed in acetone to confirm that the unexposed portion of the coating film was dissolved, and that the exposed portion of the coating film was cured and did not dissolve. Further, it was immersed in a 5% aqueous solution of sodium hydroxide at 40 ° C., and it was confirmed that the unexposed portion of the coating film was dissolved, and that the exposed portion of the coating film was cured and did not dissolve. 26 in the exposed part (cured part)
When a soldering iron adjusted to 0 ° C. was applied for 5 seconds, the cured coating film swelled and partly peeled off from the aluminum plate.

[0054]

According to the present invention, there is provided a photosensitive resin composition which is free from coloring over time, becomes thickened and gelled, has excellent storage stability, and gives a cured product having excellent heat resistance.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 216/12 C08F 216/12 220/06 220/06 222/08 222/08 299/06 299/06 G03F 7/028 G03F 7/028 ( 72) Inventor Masao Ishii 36, Towada, Kamisu-cho, Kashima-gun, Ibaraki Prefecture Kuraray Co., Ltd.

Claims (1)

[Claims] 1. A composition comprising (A) a structural unit (I) composed of styrene, a vinyl ether compound or an α-olefin, a maleic anhydride unit (II) and a (meth) acrylate unit (III), and their composition molar ratios Is a [structural unit (I) composed of styrene, vinyl ether compound or α-olefin]: [maleic anhydride unit (I
I)]: [(meth) acrylate unit (III)]
= 1: 0.9-1.1: 0.2-1.5 and a glass transition temperature (Tg) of 90 ° C. or more was obtained by the following general formula (1). (Wherein R ¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ² represents an alkylene group having 1 to 3 carbon atoms). A) a photosensitive resin composition comprising a diluent and (C) a photopolymerization initiator.