JP3132331B2 - Photosensitive resin and photosensitive 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 photosensitive resin composition having a high resolution and a high heat resistance for forming a protective film, which can be used in fields such as the production of printed wiring boards and precision metal working. A photosensitive resin to be obtained.

[0002]

2. Description of the Related Art In recent years, progress in the technical field of semiconductors has been remarkable, and with this, integrated circuits have entered the era of LSIs to super LSIs, and electronic devices have been rapidly reduced in size, weight, performance, and multifunctionality. . Corresponding to this trend, printed wiring boards have also been increasing in density, wiring, and surface mounting of components,
Further, higher precision and higher performance than ever before are required.

In order to meet this demand, various studies have been made on solder resists and methods of forming solder resists, but they have not yet been satisfactory. For example, silk-screen printing, which has been widely used for consumer use because of its high processing capacity and easy operation, has been used for printing by bleeding, bleeding, sagging, and expanding and contracting the screen. Accuracy is a problem, and it is no longer possible to cope with recent production of high-density printed wiring boards. Therefore, a photo solder resist method for forming a pattern by a photographic method has been developed.

In this photo solder resist method, for example, a film of a developable photosensitive resin composition is formed on a substrate,
This is a method in which pattern exposure is performed on the film and developed to remove exposed or unexposed portions to form a solder resist. The photo solder resist method includes a dry film photo solder resist method in which a photosensitive dry film is attached to a substrate and a liquid photo solder resist method in which a liquid photosensitive resin composition is applied to a substrate.

[0005]

However, this photo solder resist method has a problem to be solved. That is,
In the above-mentioned photo solder resist method using a dry film, the embedding property between circuits or pads is poor, bubbles remain, causing poor adhesion and reduced heat resistance, and there are still many problems in practical use in terms of performance. . On the other hand, the liquid photo solder resist method is roughly classified into an organic solvent development type and an alkali development type, but the organic solvent development type has environmental pollution and work environment problems. However, its performance was not enough to cope with recent high-density patterning technology.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and its object is to provide high heat resistance and high resolution, as well as adhesion to a substrate, electrical characteristics, and mechanical characteristics. An object of the present invention is to provide an excellent photosensitive resin composition that can be used as a photo solder resist that can be developed with an aqueous alkali solution, and a novel photosensitive resin that can be used for the photosensitive resin composition.

[0007]

The above object is achieved by the following general formula (1)

[0008]

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(Wherein R ₁ and R ₂ are a hydrogen atom and have 1 to 1 carbon atoms)
5 is selected from the group consisting of an alkyl group and a halogen atom, R ₃ is a hydrogen atom or a methyl group, and X is —CO—, —SO ₂ —, —CH ₂ —, —C (CF
_{3) 2 -, - Si (} CH 3) 2 -, - C (CH 3) 2 -, - O
Y represents a residue having a free carboxyl group of a saturated or unsaturated polybasic anhydride, and n represents 1
This can be solved by providing an alkali-developable photosensitive resin represented by the following integer:

This photosensitive resin is saturated with an epoxy acrylate intermediate obtained by, for example, reacting a hydroxyl group of a bisphenol type epoxy resin with isocyanatoethyl (meth) acrylate and reacting the epoxy group with (meth) acrylic acid. Alternatively, it can be produced by reacting with an unsaturated polybasic acid anhydride. This epoxy acrylate intermediate is used in an amount of at least 0.3 equivalent of isocyanatoethyl (meth) per hydroxyl group of the bisphenol type epoxy resin.
The photosensitive resin is obtained by reacting an acrylate with an epoxy acrylate.
It is preferable that 5 or more equivalents of a saturated or unsaturated polybasic acid anhydride are reacted. The photosensitive resin of the present invention has an acid value of 30 mgKOH / g to 150 mgKOH.
/ G is preferable.

The present invention also relates to the above photosensitive resin (hereinafter referred to as “photosensitive resin”).
The photosensitive resin A10 containing an epoxy compound having at least one epoxy group in the molecule (hereinafter referred to as “epoxy compound B”).
Provided is an alkali-developable photosensitive resin composition (hereinafter, referred to as "the present composition") in which the ratio of epoxy compound B to 0 part by weight is in the range of 10 parts by weight to 55 parts by weight. The composition preferably contains 0.5 to 30 parts by weight of a photopolymerization initiator and / or a sensitizer (hereinafter, referred to as "initiator C") per 100 parts by weight of the photosensitive resin A. .

Next, the photosensitive resin A of the present invention will be described in detail. The photosensitive resin A represented by the general formula (1) is a novel compound having a bisphenol-type epoxy resin as a skeleton, an isocyanatoethyl (meth) acrylate residue in a side chain thereof, and a terminal of the molecule. It has a structural feature in that it has a polymerizable ethylene group and a free carboxyl group derived from a polybasic acid anhydride residue.

The photosensitive resin A is alkali-soluble and photopolymerizable. Then, the photopolymer becomes insoluble in alkali. The photosensitive resin A and its photopolymer react with an epoxy compound B having at least one epoxy group in a molecule under heating to give a cured product. This cured product has high heat resistance, adhesion to substrates, etc.
It was found that the electrical and mechanical properties were also excellent. Further, it was found that a resist pattern having extremely excellent resolution can be obtained by forming a film on a substrate using the present composition containing the photosensitive resin A and the epoxy compound B, and performing pattern exposure and alkali development. The invention has been reached.

In the photosensitive resin A represented by the general formula (1),
Examples of the bisphenol residue where X is -CO- include:
For example, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, and the like can be given. X is -SO ₂ -
Examples of the bisphenol residue are, for example, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, etc. Can be mentioned. X is -CH ₂ - Examples of bisphenol residues are, for example, bis (4-hydroxyphenyl) methane, bis (4-hydroxy -
3,5-dimethylphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane and the like can be mentioned. Examples of the bisphenol residue in which X is —C (CF ₃ ) ₂ — include, for example, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, Bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane and the like can be mentioned. Examples of the bisphenol residue in which X is —Si (CH ₃ ) ₂ — include, for example, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-
Examples thereof include dimethylphenyl) dimethylsilane and bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane. Examples of the bisphenol residue in which X is —C (CH ₃ ) ₂ — include, for example, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethyl) Phenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-
3-Methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane and the like can be mentioned. Examples of the bisphenol residue in which X is -O- include, for example, bis (4-hydroxyphenyl)
Ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether and the like can be mentioned.
Examples of bisphenol residues in which X represents a direct bond include:
For example, 4,4'-biphenol, 3,3'-biphenol and the like can be mentioned. Of course, the bisphenol residue contained in the photosensitive resin A of the present invention is not limited to the above examples. Further, these bisphenol residues may be present in a molecule or in a molecule.

In the photosensitive resin A represented by the general formula (1), Y represents a residue of a saturated or unsaturated polybasic acid anhydride having a free carboxyl group. Examples of acid anhydrides that can be used include maleic anhydride, succinic anhydride,
Itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endmethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride,
Dibasic acid anhydrides such as chlorendic anhydride and methyltetrahydrophthalic anhydride; aromatic polycarboxylic anhydrides such as trimellitic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic dianhydride;
Examples thereof include polycarboxylic anhydride derivatives such as-(2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.

The photosensitive resin A uses a bisphenol type epoxy resin as a starting material, a hydroxyl group in a side chain thereof is reacted with isocyanatoethyl (meth) acrylate, and an epoxy group at a terminal thereof is substituted with (meth) acrylic acid. And an epoxy acrylate intermediate (hereinafter "intermediate b")
) And reacting this intermediate b with a saturated or unsaturated polybasic acid anhydride.

In this production, it is preferable to react at least 0.3 equivalent of isocyanatoethyl (meth) acrylate per hydroxyl group of the starting bisphenol type epoxy resin. If the amount is less than 0.3 equivalent, the physical properties of the cured film, for example, heat resistance and solvent resistance become insufficient, which is not preferable.
From this viewpoint, it is more preferable that the isocyanatoethyl (meth) acrylate is reacted in a range of 0.5 equivalent to 1.0 equivalent per hydroxyl group of the bisphenol-type epoxy resin. Further, it is preferable to react the saturated or unsaturated polybasic acid anhydride in an amount of 0.5 equivalent or more per hydroxyl group of the intermediate b. If the amount is less than 0.5 equivalent, it is insufficient and unfavorable for developing the alkali developability, which is the object of the present invention.
In this respect, it is more preferable that the saturated or unsaturated polybasic acid anhydride be reacted in a range of 0.8 equivalent to 1.0 equivalent per hydroxyl group of the intermediate b.

In order to explain the method for producing the photosensitive resin A in more detail, an example in which a bisphenol A type epoxy resin is used as a starting material bisphenol type epoxy resin will be described below. However, it goes without saying that the photosensitive resin A of the present invention is not limited to this. The bisphenol A type epoxy resin has a structure represented by the following general formula (2).

[0019]

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First, an isocyanatoethyl (meth) acrylate having the structure represented by the general formula (3) is added to the hydroxyl group of the bisphenol A type epoxy resin represented by the formula (2) to form an intermediate of the structure represented by the general formula (4). The body a is manufactured.

[0021]

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[0022]

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Next, the epoxy group of the intermediate a is reacted with (meth) acrylic acid represented by the general formula (5) to give a bisphenol A type epoxy acrylate intermediate represented by the general formula (6) (intermediate b) To manufacture.

[0024]

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[0025]

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Then, the intermediate b is reacted with the above-mentioned acid anhydride by heating in a solvent such as a ketone or cellosolve to obtain a bisphenol A type photosensitive resin represented by the general formula (1). can get. At this time, the acid value of the obtained photosensitive resin A was adjusted to 30 mgKOH / g by adjusting the reaction equivalent of the acid anhydride to the intermediate b.
To 150 mgKOH / g. For this reason, it is desirable that the reaction between the intermediate b and the acid anhydride be performed quantitatively.
This is achieved by heating to The above production method is not limited to the bisphenol A type, but can be applied to other bisphenol types in substantially the same manner.

The photosensitive resin A of the present invention preferably has an acid value in the range of 30 mgKOH / g to 150 mgKOH / g. Acid value is 30mgKOH
/ G is insufficient to develop the high resolution which is the object of the present invention, and the acid value is 150 mgKOH /
When the value exceeds g, the photocured coating is likely to swell due to the development treatment after exposure. From this viewpoint, the acid value is 50 mgKOH /
More preferably, it is within the range of g to 120 mgKOH / g.

Next, the photosensitive resin composition (the present composition) containing the photosensitive resin A and the epoxy compound B will be described. This composition basically contains a photosensitive resin A and an epoxy compound B having at least one epoxy group in a molecule. In practice, the composition further contains a photopolymerization initiator and / or a sensitizer (initiator). It preferably comprises agent C).

The epoxy compound B constituting the present composition in combination with the photosensitive resin A may be a polymer or a monomer as long as it has at least one epoxy group in the molecule. Epoxy compound B which is a polymer
Examples of epoxy resins include epoxy resins such as phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, biphenyl epoxy resin, and alicyclic epoxy resin. Can be mentioned. Examples of the epoxy compound B as a monomer include phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, glycidyl methacrylate, and the like.

When the epoxy compound B is blended in the present composition, it reacts with the photosensitive resin A or the photopolymer of the photosensitive resin A when heated to produce a tough, heat-resistant, and chemically-resistant cured product. give. This cured product also has the property of strongly adhering to a glass epoxy resin substrate, a copper plate, or the like.

The epoxy compound B is a photosensitive resin A100
It is blended in the present composition within a range of 10 parts by weight to 55 parts by weight based on parts by weight. If the amount is less than 10 parts by weight, the properties after curing of the composition of the present invention, particularly the alkali resistance, will be insufficient, and if it exceeds 55 parts by weight, cracks will occur at the time of curing and the adhesion will be reduced, which is inconvenient. is there. In this respect, a particularly preferable mixing ratio is the photosensitive resin A100.
It is in the range of 10 to 30 parts by weight with respect to parts by weight.

The present composition preferably contains an initiator C such that crosslinking polymerization occurs by exposure to low energy for a relatively short time. As the initiator C, any compound generally used for initiating photopolymerization of a photosensitive resin and accelerating the photopolymerization reaction can be used.
Examples thereof include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone,
acetophenones such as p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, pt-butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone; benzyl, benzoin, Benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzyl dimethyl ketal; thioxanthone, 2-chlorothioxanthone,
Sulfur-containing compounds such as 2,4-diethylthioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone; 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone,
Anthraquinones such as 3-diphenylanthraquinone; azobisisobutyronitrile; organic peroxides such as benzoyl peroxide and cumene peroxide;
Thiols such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole can be mentioned. These compounds may be used in combination of two or more.

In addition, a compound which does not act as a photopolymerization initiator by itself, but can increase the efficacy of the photopolymerization initiator when used in combination with the above compounds, may be added. Examples of this type of compound include, for example, tertiary amines such as triethanolamine, which are effective when used in combination with benzophenones.

The initiator C is preferably incorporated into the composition in an amount of 0.5 to 30 parts by weight per 100 parts by weight of the photosensitive resin A. If the amount is less than 0.5 part by weight, the photopolymerization rate of the composition is too low to be practical. If the amount exceeds 30 parts by weight, light hardly reaches the substrate, and the adhesion between the substrate and the resin film may be impaired. From this perspective,
A particularly desirable compounding ratio is in the range of 1 part by weight to 20 parts by weight based on 100 parts by weight of the photosensitive resin A.

The composition may further contain, if necessary, an epoxy group curing accelerator, a thermal polymerization inhibitor, a plasticizer, a leveling agent,
An additive such as an antifoaming agent may be included. Among them, examples of the epoxy group curing accelerator include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, and methylol-containing compounds. If a small amount of these epoxy group hardening accelerators is added alone or in combination to the present composition, the coating film is heated, and the resulting resist coating has heat resistance, solvent resistance, acid resistance, and plating resistance. Various properties such as properties, adhesion, electrical properties, and hardness can be improved.

Examples of the thermal polymerization inhibitor that can be added to the composition include hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, and phenothiazine. As the plasticizer, dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like can be used. Antifoaming agents, as a leveling agent, for example, silicone-based, fluorine-based,
An acrylic compound or the like is used.

The composition may further comprise, if necessary, silicon oxide,
It may contain a known filler such as talc, clay, calcium carbonate, barium sulfate, or a known coloring amount such as phthalocyanine blue, phthalocyanine green, titanium oxide, or carbon black.

The production of the present composition can be carried out by uniformly mixing the above components in the presence or absence of a solvent. When a solvent is used, ketones such as methyl ethyl ketone and methyl isobutyl ketone, cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and cellosolve acetate, or a mixture thereof can be suitably used. Needless to say, when the present composition is used as a coating liquid, it is preferable that the composition is once formed into a solution or a viscous liquid by using the above-mentioned solvent when forming a dry film.

Next, a method for forming a resist film on a substrate using the present composition will be described. In the following description, an example in which the present composition is used in the form of a solution will be described. However, when a dry film is used, the treatment can be performed in essentially the same manner according to a conventional dry film processing method.

Before the composition of the present invention is applied to a substrate, the composition is adjusted with a solvent so as to have a concentration suitable for forming a film, and if necessary, an additional photopolymerization initiator, a photopolymerization initiation auxiliary agent, and a coupling agent. A resist solution is prepared by adding an agent, an antioxidant and the like. Next, this resist solution is applied to the substrate. As a coating method, any coating method conventionally used in this field, such as dip coating, spray coating, knife coating, roller coating, bar coating, and spin coating, can be used. It is preferable that the coating thickness of the resist liquid is 1 μm to 50 μm.

The coating of the resist solution applied to the substrate is subjected to pre-curing to evaporate the solvent. This precuring is preferably performed at a temperature in the range of 40 ° C to 110 ° C. Next, a photomask is closely attached on the coating film, and ultraviolet light exposure is performed. Light sources suitable for ultraviolet exposure include an ultra-high pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp.

The exposed coating film is brought into contact with an aqueous alkali solution to carry out alkali development. Examples of the developer suitable for the alkali development include an aqueous solution of an alkali metal or alkaline earth metal carbonate, and an aqueous solution of an alkali metal hydroxide. In particular, carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate are preferable. When a weak alkaline aqueous solution containing these carbonates in an amount of 1 to 3% by weight is used, a fine image can be precisely developed. Development temperature is 10 ° C to 50 ° C, especially 20 ° C to 40 ° C
It is preferable that This development can be performed using a commercially available developing machine or an ultrasonic cleaning machine. As a result, a resist pattern is formed on the substrate by the coating film of the present composition. After the alkali development, the substrate on which the resist pattern has been formed is sufficiently washed with water.

The resist pattern obtained here is preferably subjected to post cure. In this post cure, the coating is completely dried, and at this stage, the free epoxy groups still remaining are reacted by heating to complete the curing, and the alkali resistance, solvent resistance, heat resistance, glass and This is performed to improve various properties such as adhesion to metal such as copper, surface hardness, and transparency to, for example, a high level required for a solder resist. The post-curing is preferably performed, for example, at a temperature of 80 ° C to 200 ° C for 10 minutes to 120 minutes.

[0044]

Examples of the present invention will be described below. In the following description, "parts" indicates parts by weight unless otherwise specified. (Production of photosensitive resin A)

Example 1 In a 300 ml four-necked flask, 45 g of bisphenol A type epoxy resin (Epicoat 1001 manufactured by Yuka Shell Epoxy Co., Ltd.), 1 g of dibutyltin diacetate and 45 g of dry methyl isobutyl ketone
And heated and stirred at 70 ° C. under a nitrogen stream to dissolve the resin. Next, 43 g of the compound of the formula (3) wherein R ₃ is a methyl group was added dropwise together with the same amount of dry methyl isobutyl ketone over 1 hour. Then, IR
Heating and stirring were continued until the absorption derived from the isocyanate disappeared in the spectrum to obtain a 50% solution of the intermediate a represented by the general formula (4) in methyl isobutyl ketone.

In a 300 ml four-necked flask, 177 g of a 50% solution of the above intermediate a in methyl isobutyl ketone
, A catalytic amount of p-methoxyphenol and benzyltriethylammonium chloride was added thereto, and the mixture was heated to 110 ° C while stirring under an air stream, and kept at this temperature at 7.2.
g of acrylic acid was added dropwise together with 7.2 g of methyl isobutyl ketone over 1 hour. Thereafter, stirring was continued at 110 ° C. for about 10 hours to adjust the acid value of the reaction system to 1 mg KOH / g.
Then, a 50% solution of the intermediate b represented by the general formula (6) in methyl isobutyl ketone was obtained.

In a 300 ml four-necked flask, a 50% solution of the above intermediate b in methyl isobutyl ketone 191.4
g, 16 g of tetrahydrophthalic anhydride and the same amount of methyl isobutyl ketone were added, and the mixture was heated to 110 ° C. with stirring, and while maintaining this temperature, the acid value of the reaction system was 63 mgK.
Stirring was continued until the amount dropped to about OH / g, and the photosensitive resin A of Example 1 represented by the general formula (1) was produced as a 50% solution in methyl isobutyl ketone.

Example 2 The photosensitive resin of Example 2 represented by the general formula (1) was prepared in the same manner as in Example 1 except that pyromellitic anhydride was used instead of tetrahydrophthalic anhydride in Example 1. A in methyl isobutyl ketone 50%
Manufactured as a solution.

Example 3 The photosensitivity of Example 3 represented by the general formula (1) was obtained in the same manner as in Example 1 except that hexahydrophthalic anhydride was used instead of tetrahydrophthalic anhydride in Example 1. Resin A was prepared as a 50% solution in methyl isobutyl ketone.

Example 4 The procedure of Example 1 was repeated, except that phthalic anhydride was used instead of tetrahydrophthalic anhydride in Example 1, and the photosensitive resin A of Example 4 represented by the general formula (1) was used. Was prepared as a 50% solution in methyl isobutyl ketone.

Example 5 The same procedure as in Example 1 was carried out except that methylendmethylenetetrahydrophthalic anhydride was used instead of tetrahydrophthalic anhydride in Example 1, to obtain the compound of Example 5 represented by the general formula (1). Photosensitive resin A was prepared as a 50% solution in methyl isobutyl ketone.

(Production of photosensitive resin of comparative example) For comparison, the following photosensitive resin was produced. Comparative Example 1 Comparative Example 1 was carried out in the same manner as in Example 1 except that the intermediate a in Example 1 was replaced with a bisphenol A type epoxy resin (Epicoat 1001) containing no isocyanatoethyl methacrylate residue. Was prepared as a 50% solution in methyl isobutyl ketone.

Comparative Example 2 The procedure of Example 2 was repeated, except that the bisphenol A type epoxy resin containing no isocyanatoethyl methacrylate residue (Epicoat 1001) was used instead of the intermediate a in Example 2. The photosensitive resin of Comparative Example 2 was prepared as a 50% solution in methyl isobutyl ketone.

(Preparation of the present composition) The solution of the photosensitive resin A obtained in Examples 1 to 5 and at least 1
Compound B having two epoxy groups and initiator C
And an organic solvent for concentration adjustment were mixed at the following ratio to prepare a solder resist solution.

(Example 6) 40 parts of a 50% methyl isobutyl ketone solution of Example 1 Novolak type epoxy resin EOCN-4400 (Nippon Kayaku) 5 parts Darocure 1173 (Ciba Geigy) 2 parts Methyl isobutyl ketone 5 parts

(Example 7) 40 parts of the 50% methyl isobutyl ketone solution of Example 2 Novolak type epoxy resin EOCN-4400 (Nippon Kayaku) 5 parts Darocure 1173 (Ciba Geigy) 2 parts Methyl isobutyl ketone 5 parts

(Example 8) 40 parts of a 50% methyl isobutyl ketone solution of Example 3 Novolak type epoxy resin EOCN-4400 (manufactured by Nippon Kayaku) 5 parts Darocure 1173 (manufactured by Ciba Geigy) 2 parts Methyl isobutyl ketone 5 parts

(Example 9) 40 parts of 50% methyl isobutyl ketone solution of Example 4 Novolak type epoxy resin EOCN-4400 (Nippon Kayaku Co., Ltd.) 5 parts Darocure 1173 (Ciba Geigy) 2 parts Methyl isobutyl ketone 5 parts

Example 10 40% 50% methyl isobutyl ketone solution of Example 5 Novolak epoxy resin EOCN-4400 (Nippon Kayaku) 5 parts Darocure 1173 (Ciba Geigy) 2 parts Methyl isobutyl ketone 5 parts

(Preparation of Comparative Example Composition) The solutions of the photosensitive resins obtained in Comparative Examples 1 and 2, the above-mentioned epoxy compound B, the above-mentioned initiator C, and the organic solvent were prepared in the following proportions. To produce the composition solutions of Comparative Examples 3 and 4.

Comparative Example 3 50% methyl isobutyl ketone solution of Comparative Example 1 40 parts Novolak type epoxy resin EOCN-4400 (Nippon Kayaku) 5 parts Darocure 1173 (Ciba Geigy) 2 parts Methyl isobutyl ketone 5 parts

(Comparative Example 4) 40 parts of 50% methyl isobutyl ketone solution of Comparative Example 2 Novolak type epoxy resin EOCN-4400 (manufactured by Nippon Kayaku) 5 parts Darocure 1173 (manufactured by Ciba Geigy) 2 parts methyl isobutyl ketone 5 parts

(Test Example) An evaluation test as a solder resist was performed for each of the compositions of Examples 6 to 10 and each of the compositions of Comparative Examples 3 and 4. Each of the above compositions is applied to a degreased and washed copper-clad glass epoxy substrate to a thickness of about 50 μm, dried, and irradiated with ultraviolet rays of 500 mJ / cm ² through a photomask having a pattern with a line width of 50 μm. And exposed to light. Next, 25% using 1% aqueous solution of iminodiethanol.
Developing at 1 ° C. for 1 minute to remove unexposed portions. Then, it was put in a drying oven and post-cured at 150 ° C. for 1 hour.

The obtained samples were evaluated for heat resistance, substrate adhesion and resolution as follows. Heat resistance: After the post-cured sample was left in an oven at 250 ° C. for 2 hours, the state of the film was observed. The evaluation results were indicated by を for no abnormality, Δ for slight deformation, and × for crack, peeling or coloring. Substrate adhesion: at least 1 on the post-cured sample
A cross cut was made so as to make 00 grids, and a peeling test using cellophane tape was performed. The evaluation results are indicated by ○ when no peeling was observed, and by X when slight peeling was observed. Resolution: With respect to each sample exposed and developed using a photomask having a line width of 50 μm, も の indicates that the line was well formed, and △ indicates that disturbance or flow was recognized at the line.
Those whose line width of 0 μm could not be resolved were indicated by x. Table 1 shows the results.

[0065]

[Table 1]

As is clear from Table 1 above, Example 6
The samples of Examples to 10 satisfied the target quality characteristics in all of heat resistance, substrate adhesion, and resolution. On the other hand, the samples of Comparative Examples 3 and 4 using a photosensitive resin containing no isocyanatoethyl methacrylate residue did not achieve the target quality in heat resistance and were slightly inferior in resolution.

[0067]

The photosensitive resin A of the present invention has a bisphenol type epoxy resin as a skeleton and has an isocyanatoethyl (meth) acrylate residue, a photopolymerizable ethylene double bond, and a free carboxyl group. Therefore, while being photopolymerizable, the unexposed portions are alkali-soluble and the photopolymer has high heat resistance. Further, since the photosensitive resin A has a carboxyl group, it is epoxy-reactive, and when reacted with the epoxy compound B, a film having excellent heat resistance, substrate adhesion, resolution, and electrical insulation is formed. Accordingly, the photosensitive resin A of the present invention, and the present composition containing the photosensitive resin A and the epoxy compound B can be used for a solder resist, an etching resist, an interlayer insulating material, a photosensitive adhesive, a photosensitive paint, It can be used in a wide range of fields as a photosensitive material for screen printing and a photosensitive film-forming material. In particular, when the present composition is used as a solder resist, there is an advantage that it can be used as an insulating layer without peeling off from the substrate even after the soldering is completed.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI H05K 3/28 H05K 3/28 D (72) Inventor Kenji Kawamoto 1-5-1, Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd. (56) References JP-A-63-75023 (JP, A) JP-A-2-123359 (JP, A) JP-A-6-230571 (JP, A) JP-A-5-32746 (JP, A) (58) Survey Field (Int.Cl. ⁷ , DB name) G03F 7/027 C08F 299/02 C08G 59/14 G03F 7/038 H05K 3/28

Claims (5)

(57) [Claims] [Claim 1] The following general formula (1) (Wherein, R ₁ and R ₂ are any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a halogen atom, R ₃ is a hydrogen atom or a methyl group, and X is- CO
_{-, - SO 2 -, -} CH 2 -, - C (CF 3) 2 -, - Si
(CH ₃ ) ₂ —, —C (CH ₃ ) ₂ —, —O— or a direct bond, Y represents a residue having a free carboxyl group of a saturated or unsaturated polybasic acid anhydride, and n represents 1 or more And an alkali-developable photosensitive resin represented by the following formula: 2. The photosensitive resin according to claim 1, wherein the hydroxyl group of the bisphenol-type epoxy resin is isocyanatoethyl (meth).
An epoxy acrylate intermediate obtained by reacting the acrylate with an acrylate and the epoxy group thereof with (meth) acrylic acid, and a saturated or unsaturated polybasic acid anhydride, The acrylate intermediate is obtained by reacting at least 0.3 equivalents of isocyanatoethyl (meth) acrylate per hydroxyl group of the bisphenol-type epoxy resin, and the photosensitive resin has 0.5 equivalents per hydroxyl group of the epoxy acrylate intermediate. 2. The alkali-developable photosensitive resin according to claim 1, wherein said saturated or unsaturated polybasic acid anhydride is reacted. 3. An acid value of 30 mg KOH / g to 150 mg
3. The method according to claim 1, wherein the amount is in the range of mgKOH / g.
3. The photosensitive resin capable of being alkali-developed according to item 2. 4. The photosensitive resin according to claim 1, further comprising: an epoxy compound having at least one epoxy group in a molecule, based on 100 parts by weight of the photosensitive resin. When the ratio of the epoxy compound is 1
An alkali developable photosensitive resin composition in the range of 0 to 55 parts by weight. 5. A photopolymerization initiator and / or a sensitizer are added in an amount of 0.5 to 30 parts by weight per 100 parts by weight of the photosensitive resin.
5. The alkali developable composition according to claim 4, wherein the content is within the range of parts by weight.
Functional photosensitive resin composition.