JP2000298340A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To attain excellent developability, curability and tackiness and to allow an exposed part to have durability in a developer by using a copolymer containing units derived from a specified polysiloxane-containing acrylic acid or methacrylic acid derivative and a specified prepolymer. SOLUTION: The photosensitive resin composition consists of a copolymer containing 1-40 wt.% units derived from a polysiloxane-containing acrylic acid or methacrylic acid derivative of the formula, 5-50 wt.% units derived from an unsaturated monomer having a carboxyl group and 10-94 wt.% units derived from an unsaturated monomer copolymerizable with the above monomers and a prepolymer having at least one polymerizable unsaturated group and one or more carboxyl group in one molecule. The copolymer is contained by 0.1-100 pts.wt. based on 100 pts.wt. prepolymer. In the formula, R1 is H or methyl, R2 is 1-8C alkylene, R3, R3' and R4 are each H, phenyl or the like and (m) is an integer of 1-150.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a photosensitive resin composition. For details, photosensitive resin composition for solder resist film for printed wiring boards and insulating resin layer for various electronic components with excellent properties such as developability, curability, tackiness, adhesion, heat resistance and chemical resistance About things.

[0002]

2. Description of the Related Art In a printed wiring board, a solder resist is widely used as a permanent protective film of a circuit. Solder resist is a coating that is formed on the entire surface of the circuit conductor except for the parts to be soldered.When wiring electronic components on a printed wiring board, it prevents solder from adhering to unnecessary parts and Is used as a protective coating to prevent direct exposure to air. At present, liquid solder resist inks are widely used as solder resists for printed wiring boards from the viewpoints of high precision, high density, and environmental issues.

As a liquid solder resist ink, for example, JP-A-60-208337 and JP-A-61-59447 disclose a solder containing a novolak-type epoxy resin partially reacted with acrylic acid as a main component. Resist ink compositions have been proposed. However, these ink compositions have insufficient curing properties after exposure,
There were problems such as stickiness (tack) remaining after the coating film was formed. Japanese Patent Publication No. 1-54390 proposes a photosensitive resin composition containing, as a main component, a reaction product of an adduct of a novolak epoxy resin with an unsaturated monocarboxylic acid and a polybasic acid anhydride. . However, when the ink is left for a long time, the photosensitive resin composition may cause uneven development in unexposed areas, may become sticky after forming the coating film, and the pattern film may not be peeled off, or a part of the resist may be removed. There was a problem that a correct pattern could not be obtained due to adhesion to the film. Japanese Patent Application Laid-Open No. 6-168443 discloses a photopolymerizable resin having a high molecular weight obtained by reacting a reaction product of a novolak type epoxy resin with (meth) acrylic acid with a chain extender. However, even with this photopolymerizable resin, tackiness after formation of a coating film was not sufficient. As described above, a photosensitive resin composition for a solder resist having all favorable properties such as developability, curability and tackiness has not yet been obtained.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned various problems and provides an energy-ray-curable photosensitive material having excellent developability, curability and tackiness and having resistance to a developing solution in an exposed portion. An object of the present invention is to provide a conductive resin composition. Further, in the present invention, in addition to the above-mentioned various properties, a cured coating film having excellent adhesion, electrical insulation, solder heat resistance, solvent resistance, acid resistance, alkali resistance, plating resistance, etc. required for a solder resist. It is an object of the present invention to provide a photosensitive resin composition having characteristics capable of forming a resin and suitable for manufacturing a printed wiring board and the like.

[0005]

Means for Solving the Problems In order to solve these problems, the present inventors have made intensive studies and as a result, have found that a copolymer which is alkali-soluble and has good tackiness and a photopolymerizable prepolymer It has been found that a photosensitive resin composition excellent in developability, curability, tackiness, adhesion, heat resistance and chemical resistance can be obtained by combining the above, and the present invention has been completed. That is, the gist of the present invention is a unit (a1) derived from a polysiloxane group-containing acrylic acid or methacrylic acid derivative represented by the formula (1), a unit (a2) derived from an unsaturated monomer having a carboxyl group, and Units (a3) derived from copolymerizable unsaturated monomers are represented by a1:
0% by weight, a2: 5 to 50% by weight, a3: 10 to 94% by weight (provided that the entire copolymer is 100% by weight), and at least one copolymer in the molecule. A prepolymer (B) having a polymerizable unsaturated group and at least one carboxyl group;
The photosensitive resin composition contains 0.1 to 100 parts by weight of the copolymer (A) per part by weight.

[0006]

Embedded image

(Where R ¹ is a hydrogen atom or a methyl group,
R ² is an alkylene group having 1 to 8 carbon atoms, R ³ and R ³ ′ are a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, a polyoxyalkylene group, and a polyether terminated with an ether or ester. R ⁴ represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, a polyoxyalkylene group, a terminal of which is substituted with an ether or ester; an oxyalkylene group, a polyalkylene polyamine group, a fatty acid group, or a polysiloxane group; A polyoxyalkylene group, a polyalkylene polyamine group, a fatty acid group, a polysiloxane group, a vinyl group, a vinylalkylene group, a vinylhydroxyalkylene group, an acryloyloxyalkylene group or a methacryloyloxyalkylene group. m is an integer of 1 to 150. )

The gist of the present invention is that, in addition to the above components, 1 to 30 parts by weight of a photopolymerization initiator (C) and 100 parts by weight of a reactive diluent (D) per 100 parts by weight of the prepolymer (B)
1 to 100 parts by weight and the epoxy resin (E) is 2-1.
It is also present in the above photosensitive resin composition containing 00 parts by weight. Another gist of the present invention is that the unit (a2) derived from the unsaturated monomer having a carboxyl group in the structural unit of the copolymer (A) is a compound having an unsaturated monomer having a hydroxyl group and an acid anhydride. The above-mentioned photosensitive resin composition obtained by the reaction of the above, and the prepolymer (B) is obtained by reacting a reaction product of an epoxy compound and an unsaturated monocarboxylic acid with a polybasic acid anhydride. Or prepolymer (B)
Has a carboxyl group formed by the reaction of a reaction product of an epoxy compound with an unsaturated monocarboxylic acid and a polybasic acid anhydride, and further has one epoxy group and one or more unsaturated groups in the molecule. The photosensitive resin composition obtained by reacting the compound also exists in the above-mentioned photosensitive resin composition. Further, another gist of the present invention is that the unit (a3) derived from an unsaturated monomer in the structural unit of the copolymer (A) is a unit derived from an unsaturated monomer having a tertiary amino group. The above-mentioned photosensitive resin composition and a photosensitive resin composition obtained by modifying the tertiary amino group with a quaternary ammonium salt also exist.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, each component and use of the photosensitive resin composition of the present invention will be described in detail. In this specification, the notation “(meth) acrylic acid” means acrylic acid or methacrylic acid, the notation “(meth) acryloyl group” means acryloyl group or methacryloyl group, and “(meth) acrylate "" Means acrylate or methacrylate.

Copolymer (A) The copolymer (A) in the photosensitive resin composition of the present invention contains three types of structural units (a1) to (a3) as described above. Among them, (a1) is based on a polysiloxane group-containing acrylic acid or methacrylic acid derivative represented by the formula (1).

[0011]

Embedded image

(Where R ¹ is a hydrogen atom or a methyl group,
R ² is an alkylene group having 1 to 8 carbon atoms, R ³ and R ³ ′ are a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, a polyoxyalkylene group, and a polyether terminated with an ether or ester. An oxyalkylene group, a polyalkylene polyamine group, a fatty acid group, or a polysiloxane group, and R ⁴ is a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, a polyoxyalkylene group, and the terminal is substituted with an ether or ester. A polyoxyalkylene group, a polyalkylene polyamine group, a fatty acid group, a polysiloxane group, a vinyl group, a vinylalkylene group, a vinylhydroxyalkylene group, an acryloyloxyalkylene group or a methacryloyloxyalkylene group. m is an integer of 1 to 150. )

(A1) is contained in the copolymer (A) in an amount of 1 to 40% by weight, more preferably 3 to 20% by weight (the whole copolymer is 100% by weight). (A1)
When the content in the copolymer is less than 1% by weight, the tackiness of the obtained photosensitive resin composition becomes insufficient, while when it exceeds 40% by weight, the developability of the photosensitive resin composition becomes insufficient. .

Another structural unit (a2) of the copolymer (A)
Is derived from an unsaturated monomer having a carboxyl group. Such compounds include acrylic acid, methacrylic acid, acrylic acid dimer, ω-carboxy-polycaprolactone monoacrylate, 2-acryloyloxyethylsuccinic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethylhexahydrophthalate Examples thereof include acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid, but are not limited thereto. Copolymer (A)
The content of the unit (a2) derived from an unsaturated monomer having a carboxyl group is 5 to 50% by weight, preferably 10 to 10% by weight.
30% by weight. The content of (a2) in the copolymer is 5
If the amount is less than 50% by weight, the developability of the obtained photosensitive resin composition will be insufficient, while if it exceeds 50% by weight, the chemical resistance will be insufficient.

The other structural unit (a3) of the copolymer (A) used in the present invention is derived from an unsaturated monomer copolymerizable with the above-mentioned components. weight%
Contained. Examples of the copolymerizable unsaturated monomer that can be used here include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl ( (Meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth)
Acrylate, n-octyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, n-lauryl (meth) acrylate, n-
Stearyl (meth) acrylate, i-stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2
-Hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate , N-butoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth)
Acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate quaternary, diethylaminoethyl (meth) acrylate quaternary, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) ) Acrylate, dimethylaminopropyl (meth) acrylate quaternary compound, diethylaminopropyl (meth) acrylate quaternary compound, 3-epoxy (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxybutyl ( (Meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, trifluoroethyl (meth) acrylate, , 2,3,3-tetrafluoro propyl (meth) acrylate, 2,2,3,4,4,4
-Hexafluorobutyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, (meth)
Acrylic acid, crotonic acid, cinnamic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth)
Acryloyloxyethyl-2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl phosphoric acid, styrene, maleic anhydride and the like can be mentioned. These polymerizable unsaturated monomers can be used alone or in combination of two or more thereof.

The content of the copolymer (A) in the photosensitive resin composition of the present invention is 0.1 to 100 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the prepolymer (B).
Parts by weight. When the content of the copolymer (A) is less than 0.1 part by weight, the tackiness of the obtained photosensitive resin composition is insufficient, and when it exceeds 100 parts by weight, the curability of the photosensitive resin composition is insufficient. Becomes The copolymer (A) is, for example,
It can be obtained by solution polymerization or emulsion polymerization. In the case of using the solution polymerization method, for example, a mixture of each monomer for (a1), (a2) and (a3) is mixed with a polymerization initiator in an organic solvent capable of dissolving these components and the obtained polymer. For example, a method of adding and stirring under heating in a nitrogen stream is used.

Examples of the organic solvent used for the solution polymerization include methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as cyclohexanone, aromatic hydrocarbons such as toluene and xylene, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, acetate esters such as propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether and the like Examples include glycol ethers, alcohols such as ethylene glycol and propylene glycol, dialkylene glycols, aliphatic hydrocarbons such as octane and nonane, and petroleum solvents such as petroleum naphtha and solvent naphtha. These solvents can be used alone or in combination of two or more. Also,
The copolymer (A) can also be produced by an emulsion polymerization method using water as a dispersion medium and a redox catalyst as a polymerization initiator in the presence of a surfactant.

Prepolymer (B) The prepolymer (B) having at least one polymerizable unsaturated group and one or more carboxyl groups in one molecule for use in the photosensitive resin composition of the present invention includes: For example, a prepolymer obtained by reacting a saturated or unsaturated polybasic anhydride with a reaction product of an epoxy resin and an unsaturated monocarboxylic acid, or a reaction product of the above-described saturated or unsaturated polybasic anhydride. And a prepolymer obtained by reacting a compound having one epoxy group and one or more unsaturated groups with the carboxyl group.

The epoxy resin used as a raw material of the prepolymer (B) includes, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, biphenyl epoxy resin, bixylenol epoxy resin, N-glycidyl type epoxy resin, triglycidyl isocyanurate, phenol novolak resin, cresol novolak resin, ethylphenol novolak resin, isopropylphenol novolak resin, tert-butylphenol novolak resin, 3,5-xylenol novolak resin, bromphenol novolak resin, bisphenol A Novolak resin, naphthalene novolak resin, glycidyl compound of polyvinylphenol, phenols and phenolic hydroxyl group And epoxy resins such as a copolymer of an alkyl (meth) acrylate and an epoxy-containing monomer such as an epoxy-containing (meth) acrylate. . Above all, novolak type epoxy resins such as phenol novolak type, cresol novolak type and bisphenol A novolak type are preferable. These epoxy resins can be used alone or in combination of two or more. Examples of the unsaturated monocarboxylic acid which is another raw material used in the synthesis of the prepolymer (B) include, for example,
(Meth) acrylic acid, crotonic acid, cinnamic acid and the like. These unsaturated carboxylic acids can be used alone or in combination of two or more.

In the reaction between the unsaturated monocarboxylic acid and the epoxy resin, it is preferable to use 0.8 to 1.2 equivalents of the unsaturated monocarboxylic acid per 1 equivalent of the epoxy group of the epoxy resin. If the unsaturated monocarboxylic acid is less than 0.8 equivalent, the stability of the photosensitive resin composition becomes insufficient,
If it exceeds 1.2 equivalents, the curability tends to be insufficient. The reaction between the epoxy resin and the unsaturated monocarboxylic acid is 100-
Preferably performed at 120 ° C.

The prepolymer (B) can be obtained by reacting a reaction product of the above epoxy resin with an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic anhydride.
Examples of the saturated or unsaturated polybasic anhydride used herein include maleic anhydride, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, -3-methylhexahydrophthalic anhydride, -4-hexanhydride Hydrophthalic acid, -3-ethylhexahydrophthalic anhydride, -4
-Ethylhexahydrophthalic acid, tetrahydrophthalic anhydride, -3-methyltetrahydrophthalic anhydride,-
4-Methyltetrahydrophthalic acid, -3-ethyltetrahydrophthalic anhydride, -4-ethyltetrahydrophthalic anhydride and the like are preferable from the viewpoint of developability and reactivity with a thermosetting component.

The amount of the saturated or unsaturated polybasic acid anhydride to be used is 0.1 to 1 equivalent of the epoxy group of the epoxy resin.
It is preferable to use 3 to 1.0 equivalent. When the amount of the saturated or unsaturated polybasic acid anhydride is less than 0.3 equivalent, the developability becomes insufficient, and when it exceeds 1.0 equivalent, the stability becomes insufficient. This reaction is preferably performed at 60 to 120 ° C. As the prepolymer (B), this reaction product can be used, but the carboxyl group generated by this reaction is used to further have one epoxy group and one or more unsaturated groups in this group. What reacted the compound may be used.

Examples of the compound having one epoxy group and one or more unsaturated groups that can be used herein include 3-epoxy groups and one or more unsaturated groups.
It has an epoxy group such as epoxypropyl (meth) acrylate, 3-epoxybutyl (meth) acrylate, 4-epoxybutyl (meth) acrylate, 3-epoxycyclohexylmethyl (meth) acrylate, and 4-epoxycyclohexylmethyl (meth) acrylate. Compounds such as (meth) acrylate and acylglycidyl ether can be exemplified. These compounds can be used alone or in combination of two or more.

The amount of the compound having one epoxy group and one or more unsaturated groups is from 0.1 to 1 equivalent of the carboxyl group derived from a saturated or unsaturated polybasic anhydride.
0.6 equivalent is preferred. In addition, this reaction is 100 to 12
It is preferably performed at 0 ° C. In the synthesis of the prepolymer (B), for example, when the obtained prepolymer is in a liquid state at room temperature, the reaction can be carried out without a solvent. However, the viscosity of the reaction system is adjusted and the mixing is sufficiently performed. The reaction is preferably performed using a solvent for the purpose of improving heat transfer. Solvents that can be used here include ketones such as methyl ethyl ketone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, glycol ethers such as methyl cellosolve, methyl carbitol and diethylene glycol dimethyl ether, ethyl acetate and ethylene glycol. Glycol ethers such as monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monobutyl ether acetate Vinegar Esters of ester compounds such as ethylene glycol, polyhydric alcohols such as propylene glycol, aliphatic hydrocarbons such as octane, petroleum naphtha, petroleum solvents such as solvent naphtha, water and the like. These solvents can be used alone or in combination of two or more. The amount of the solvent used is, for example, preferably 5 to 1000 parts by weight based on 100 parts by weight of the prepolymer (B).

Photopolymerization Initiator (C) Examples of the photopolymerization initiator (C) that can be used in the photosensitive resin composition of the present invention include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. The alkyl ethers, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone,
1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[(4-methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1
-Acetophenones such as butanone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-
Anthraquinones such as amylanthraquinone, 2,4-
Thioxanthones such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenones such as benzophenone and xanthones can be exemplified. . These photopolymerization initiators can be used alone or in combination of two or more.

The photopolymerization initiator may be used in combination with one or more benzoic acid-based or tertiary amine-based photopolymerization accelerators. Photopolymerization initiator (C)
Is used per 100 parts by weight of the prepolymer (B).
It is more preferably from 30 to 30 parts by weight, and more preferably from 3 to 25 parts by weight. When the use amount of the photopolymerization initiator (C) is less than 1 part by weight, the photocurability of the photosensitive resin composition deteriorates, and the purpose of adding the photopolymerization initiator is not sufficiently achieved. When the amount is larger than the number of parts, the characteristics as the solder resist tend to be deteriorated.

Reactive diluent (D) In order to further cure the photosensitive resin composition by energy rays to obtain a coating film having water resistance, heat resistance and alkali resistance, a reactive diluent (D) is used. Preference is given to using D). Reactive diluent (D) used in the present invention
Is a compound having at least two double bonds, for example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate,
Neopentyl glycol di (meth) acrylate hydroxypivalate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, ethylene oxide-modified di (meth) phosphate ) Acrylate, allylated cyclohexyl di (meth) acrylate, di (meth) acrylate isocyanurate, trimethylolpropane di (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, propionic acid-modified dipenta Erythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid-modified dipentaerythritol tetra (meth) acrylate, propionic acid-modified dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa ( Data) acrylate, and the like.

The above-mentioned polyfunctional reactive diluents can be used alone or
More than one species can be used in combination. The amount of the reactive diluent (D) used is preferably 1 to 100 parts by weight, more preferably 2 to 50 parts by weight, per 100 parts by weight of the prepolymer (B). When the amount of the reactive diluent (D) is 1 part by weight or less, the photocurability of the photosensitive resin composition becomes insufficient and the purpose of adding this component is not sufficiently achieved. Tend to be insufficient.

Epoxy resin (E) In order to improve the strength of the coating film after curing of the photosensitive resin composition, it is preferable to add the epoxy resin (E) to the composition. Examples of the epoxy resin that can be used here include a polyfunctional epoxy resin containing two or more epoxy groups, such as a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a biphenyl epoxy resin, and a biphenyl epoxy resin. Xylenol type epoxy resin, N-glycidyl type epoxy resin, triglycidyl isocyanurate and phenol novolak resin,
Cresol novolak resin, ethylphenol novolak resin, isopropylphenol novolak resin, te
rt-butylphenol novolak resin, 3,5-xylenol novolak resin, bromophenol novolak resin, bisphenol A novolak resin, naphthalene novolak resin, glycidyl compounds such as polyvinylphenol, condensates of phenols with aromatic aldehydes having phenolic hydroxyl groups Epoxidized products, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ethers such as tetraethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether,
Polypropylene glycol diglycidyl ethers such as tripropylene glycol diglycidyl ether, polyglycerin polyglycidyl ethers such as glycerin polyglycidyl ether, diglycerin polyglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, pentaerythritol polyglycidyl ether, Epoxy resins such as trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, and diglycidyl adipate alone or two kinds These can be used in combination. The amount of epoxy resin (E) used is
The amount is preferably 2 to 100 parts by weight, more preferably 10 to 50 parts by weight, per 100 parts by weight of the prepolymer (B). If the amount of the epoxy resin (E) is less than 2 parts by weight, the hardness of the coating film will not be sufficiently high, and the purpose of adding the epoxy resin will not be sufficiently achieved, whereas if it exceeds 100 parts by weight, the photocurability will decrease. Tend to be.

Other Additives In the photosensitive resin composition of the present invention, a solvent may be used in order to adjust the viscosity and improve the coatability and handleability.
As such a solvent, the solvent used at the time of synthesizing the copolymer (A) or the prepolymer (B), which is a component of the composition of the present invention, may be used as it is, or after removing these once, Alternatively, a solvent according to the use may be added. Examples of the solvent that can be used include those already described for the synthesis of the above components.

Further, additives can be added to the photosensitive resin composition of the present invention, if necessary, within a range not departing from the object of the present invention or impairing the effects of the present invention. Specifically, inorganic fillers such as silica, alumina, talc, clay, calcium carbonate, barium sulfate, etc.
Phthalocyanine-based, azo-based organic pigments, paint additives such as antifoaming agents, leveling agents, curing accelerators such as urea derivatives or hydroquinone, hydroquinone monomethyl ether, pyrogallol, tertiary butyl catechol, phenothiazine, N-nitrosophenyl Examples thereof include polymerization inhibitors such as hydroxylamine aluminum salt and N-nitrosophenylhydroxylamine ammonium salt.

Applications and Usage As described above, the photosensitive resin composition of the present invention is used for a solder resist film for a printed wiring board and an insulating resin layer of various electronic components. Upon use, it is applied to a metal plate such as aluminum or stainless steel, a screen mesh, paper, wood, synthetic resin, a semiconductor substrate, or any other substrate, and dried according to the intended use. In order to cure the photosensitive resin composition of the present invention, an electron beam,
Energy rays such as various kinds of ionizing radiation and light such as α rays, β rays, γ rays, X rays, neutron rays or ultraviolet rays are used.

[0033]

EXAMPLES Hereinafter, specific embodiments of the present invention will be described in more detail with reference to Examples.
The operating conditions and the like can be appropriately changed without departing from the spirit of the present invention, and therefore, the scope of the present invention is not limited by the following examples.

The copolymer (A) and the prepolymer (B)
Adult (Synthesis Example A-1) a thermometer, a flask equipped with a stirrer and a reflux condenser, and R ^1, R ³ methacryloyloxy polysiloxane as component for (a1) ( "MPS-1" formula (1) R ³ ′ is a methyl group, R ² is a propylene group, R ⁴ is a butyl group, m (average value) = 10) 15 g, 90 g of 2-methacryloyloxyethylhexahydrophthalic acid as a component for (a2), 195 g of methyl methacrylate was charged as a component, 700 g of methyl ethyl ketone as a solvent, and 6 g of azobisisobutyronitrile as a catalyst.
Was added and polymerization was carried out at 80 ° C. for 5 hours under a nitrogen stream to obtain a copolymer solution (A-1). The amount of nonvolatile components in the obtained copolymer solution was about 30%.

(Synthesis Example A-2) The components shown in Table 1 were used as the components for (a1) to (a3), and the solvent methyl ethyl ketone was used in an amount of 734 g.
The reaction was carried out in the same manner as in 1). 14.7 g of dimethyl sulfuric acid was added to the obtained reaction solution and reacted at 80 ° C. for 3 hours to obtain a copolymer solution (A-2). The amount of nonvolatile components in the obtained copolymer solution was about 30%.

(Synthesis Example A-3) The components shown in Table 1 were used as the components for (a1) to (a3), and the amount of the solvent methyl ethyl ketone used was 723 g, and the above synthesis example (A-
The reaction was carried out in the same manner as in 1). 6.9 g of acrylic acid was added to the obtained reaction solution and reacted at 80 ° C. for 3 hours to obtain a copolymer solution (A-3). The amount of nonvolatile components in the obtained copolymer solution was about 30%.

(Synthesis Example A-4) The components shown in Table 1 were used as the components for (a1) to (a3), and the amount of the solvent methyl ethyl ketone used was 817 g, and the above synthesis example (A-
The reaction was carried out in the same manner as in 1). Aronix TO-756 (manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate modified with succinic anhydride) is added to the obtained reaction solution.
50 g was added and reacted at 80 ° C. for 3 hours to obtain a copolymer solution (A
-4) was obtained. The amount of nonvolatile components in the obtained copolymer solution was about 30%.

(Synthesis Example A-5) The components shown in Table 1 were used as the components for (a1) to (a3), and the amount of the solvent methyl ethyl ketone used was 734 g.
The reaction was carried out in the same manner as in 1). 14.7 g of dimethyl sulfuric acid was added to the obtained reaction solution and reacted at 80 ° C. for 3 hours to obtain a copolymer solution (A-5). The amount of nonvolatile components in the obtained copolymer solution was about 30%.

(Synthesis Example A-6) The components shown in Table 1 were used as the components for (a1) to (a3), and the solvent methyl ethyl ketone was used in an amount of 700 g.
The reaction was carried out in the same manner as in 1). 14.7 g of diethyl sulfuric acid was added to the obtained reaction solution and reacted at 80 ° C. for 3 hours to obtain a copolymer solution (A-6). The amount of nonvolatile components in the obtained copolymer solution was about 30%.

(Synthesis Example A-7) The components for (a1) and (a2) were not used, and only the components for (a3) shown in Table 1 were used. A polymerization reaction was carried out in the same manner, and the copolymer solution (A-
7) was obtained. The amount of nonvolatile components in the obtained copolymer solution was about 30%.

(Synthesis Example A-8) Without using the components for (a1), only the components for (a2) and (a3) shown in Table 1 were used, and the amount of the solvent methyl ethyl ketone used was 700 g. A polymerization reaction was carried out in the same manner, and the copolymer solution (A-
8) was obtained. The amount of nonvolatile components in the obtained copolymer solution was about 30%.

(Synthesis Example A-9) Only the components (a1) and (a3) shown in Table 1 were used without using the component for (a2).
The polymerization reaction was carried out in the same manner as in Synthesis Example 1 except that the amount of the solvent methyl ethyl ketone used was 700 g, and the copolymer solution (A-9)
I got The amount of nonvolatile components in the obtained copolymer solution is about 30
%Met.

[0043]

[Table 1]

A1 component: R ^{1 to} R ⁴ and m of MPS-1 to 4 are as follows. ^{MPS-1 ··· R 1, R} 3, R 3 '; methyl, R ^2; propylene group, R ^4; butyl group, m (average); 10 MPS-2 ··· R 1, R 3, R ³ '; methyl group, R ² ; propylene group, R ⁴ ; butyl group, m (average value); 130 MPS-3 ··· R ¹ , R ³ , R ³ '; methyl group, R ² ; propylene group , R ^4; butyl group, m (average); 65 MPS-4 ··· R 1, R 3 ', R 4; methyl, R ^2; propylene group, R ^3; a trimethylsilyl group, m (average value) 1a2 component: 2-MEHPA ... 2-methacryloyloxyethyl hexahydrophthalic acid 2-MESA ... 2-methacryloyloxyethyl succinic acid 2-AESA ... 2-acryloyloxyethyl succinic acid MAA ... Methacrylic acid a3 component: MMA ... methyl methac Relate LMA: lauryl methacrylate DMAEMA: N, N-dimethylaminoethyl methacrylate 2EHMA: 2-ethylhexyl methacrylate SMA: stearyl methacrylate Reaction solvent: MEK: methyl ethyl ketone Reaction conditions: 80 ° C. × 5 hours Treatment: DMS: dimethyl sulfate AA: acrylic acid ANX-TO: succinic anhydride modified product of pentaerythritol triacrylate manufactured by Toagosei Co., Ltd. (trade name "Aronix TO-756")

(Synthesis Example B-1) In a flask equipped with a thermometer, a stirrer and a reflux condenser, an epoxy resin (o-cresol novolac type epoxy resin “Epicoat 180S80” manufactured by Yuka Shell Epoxy Co., Ltd.), epoxy equivalent = 21
8) After adding and dissolving 218 g and 78.5 g of diethylene glycol monoethyl ether acetate, 0.26 g of hydroquinone monomethyl ether and 0.16 N-nitrosophenylhydroxylamine aluminum salt were added.
g, 72 g of acrylic acid and triphenylphosphine
8 g was added and reacted at 110 ° C. until the acid value became 2 or less. Then, 76.1 g of tetrahydrophthalic anhydride
And petroleum-based solvents (Solvesso 15 manufactured by Exxon Chemical Co., Ltd.)
0 ") 78.5 g, and reacted at 100 ° C. for 4 hours.
A prepolymer (B-1) was obtained. The amount of nonvolatile components in this resin solution was about 70%.

(Synthesis Example B-2) The amount of tetrahydrophthalic anhydride used in Synthesis Example B-1 was 136.9 g.
After performing the same reaction as above, 42.6 g of glycidyl methacrylate was added, and the reaction was performed at 110 ° C. for 4 hours to synthesize a prepolymer (B-2). The amount of nonvolatile components in the obtained resin solution was about 60%.

(Synthesis Example B-3) In the above Synthesis Example B-1, the type of epoxy resin was changed to a bisphenol-A novolak type “Epicoat 157S7” manufactured by Yuka Shell Epoxy.
0 "(epoxy equivalent = 209),
g, and the amounts of diethylene glycol monoethyl ether acetate and triphenylphosphine were changed to 94 g and 1.4 g, respectively, except that aluminum N-nitrosophenylhydroxylamine was not added. did. Subsequently, 76.1 g of tetrahydrophthalic anhydride and 59 g of a petroleum-based solvent (“Solvesso 150” manufactured by Exxon Chemical Co., Ltd.) were added, and the mixture was added to 100 g.
The mixture was reacted at 4 ° C. for 4 hours to synthesize a prepolymer (B-3). The amount of non-volatile components in the obtained resin solution was about 70%.

Examples and Comparative Examples (Examples 1 to 10 and Comparative Examples 1 to 5)
Copolymer obtained in A-9, and Synthesis Examples B-1 to B-3
Each of the prepolymers obtained in the above was blended so as to have the composition shown in Table 2, and kneaded with a roll mill to obtain a resist ink. After applying this ink to the copper-clad laminate,
The film was dried with hot air at 30 ° C. for 30 minutes to form a 30 μm-thick coating film. The formed coating film was evaluated for developability, curability, tackiness, adhesion, solvent resistance, acid resistance, and alkali resistance according to the following procedure. Table 3 shows the evaluation results.

Evaluation method (1) Developability 1.0 kg / cm ² using 1% aqueous sodium carbonate solution
And the state of dissolution of the coating film was visually determined according to the following criteria. ：: Little paint film left on tin plate △: Little paint film left on tin plate ×: Paint film left on tin plate (2) Curable Kodak Step Tablet (UV transmittance was changed stepwise) (200 mJ / cm ² ) using a high-pressure mercury lamp through a filter plate provided with a grid.
Developed with a spray pressure of kg / cm ² for 60 seconds, and the coating film was not removed even after development. The step number was evaluated (the larger the value, the smaller the amount of UV, the more the curing progressed, and the better the curability.) did.

(3) Tackability The dried coating film was touched with a finger to determine whether or not the coating film was tacky. ：: no tack was observed at all △: fingerprint remained slightly ×: ink adhered to finger (4) Adhesion According to the test method of JIS D-2020, 1 ×
A 100 mm cross-cut of 1 mm was cut, and a peeling test was performed using cellophane tape.

(5) Solvent resistance A test piece was irradiated with 200 mJ / cm ^{2 of} ultraviolet light using a high-pressure mercury lamp, and further post-cured in an oven at 150 ° C. for 30 minutes.
After immersion at 5 ° C. for 1 hour, the state and adhesion of the coating film were comprehensively evaluated. ：: No change is observed at all △: Slight change is observed X: Notable change is observed (6) Acid resistance A test piece prepared in the same manner as in the solvent resistance evaluation was used, and 10% by volume was used. After being immersed in an aqueous hydrochloric acid solution at 25 ° C. for 1 hour, the state and adhesion of the coating film were comprehensively evaluated. ：: No change is observed at all △: Slight change is observed ×: Notable change

(7) Alkali Resistance Using a test piece prepared in the same manner as in the solvent resistance evaluation, immersing it in a 10% by weight aqueous solution of potassium hydroxide at 25 ° C. for 1 hour, and then closely contacting the state of the coating film Was evaluated comprehensively. ：: No change is observed at all △: Slight change is observed ×: Notable change

Evaluation of Results In Comparative Examples outside the scope of the present invention, there are many inferior tackiness and poor developability, durability and adhesion.

[0054]

[Table 2]

Photopolymerization initiator: Irgacure # 907 Reactive diluent: Dipentaerythritol hexaacrylate Epoxy resin: Epicoat 180S80 (manufactured by Yuka Shell Epoxy Co., Ltd.) 2-E-4-M-IZ: 2-ethyl- 4-methylimidazole

[0056]

[Table 3]

Raw materials used, abbreviations, etc. are the same as in Table 2-1.

[0058]

[Table 4]

The raw materials and abbreviations used are the same as in Table 2-1.

[0060]

[Table 5]

[0061]

The photosensitive resin composition of the present invention has a developing property,
It has excellent curability and tackiness, and is extremely useful for forming solder resist films for printed wiring boards and insulating resin layers for various electronic components.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/027 502 G03F 7/027 502 515 515 7/028 7/028 7/032 501 7/032 501 7 / 075 511 7/075 511 F-term (reference) 2H025 AA00 AA02 AA04 AA06 AA10 AA14 AA20 AB15 AC01 AD01 BC31 BC51 BC74 BC83 BC85 CB14 CB33 CB34 CB41 CB43 CB47 CB48 4J011 AA05 QA13B RA03 RA10 SA02 SA03 SA04 SA06 SA12 SA14 SA15 SA16 SA19 SA20 SA34 SA54 SA61 SA63 SA64 TA01 TA03 TA06 UA01 UA03 UA04 WA01 4J027 AC01 AC03 AC04 AC06 AE02 AE03 AE04 AE06 BA19 BA23 BA24 BA26 BA27 BA28 BA29 CA08 CA10 CA14 CA18 CC05 CC06 CC08 CD06 CD10

Claims (7)

[Claims] A unit (a) derived from a polysiloxane group-containing acrylic acid or methacrylic acid derivative represented by the formula (1)
1) a unit (a2) derived from an unsaturated monomer having a carboxyl group, and a unit (a3) derived from an unsaturated monomer copolymerizable therewith, respectively, a1: 1 to 40% by weight,
a2: 5 to 50% by weight, a3: 10 to 94% by weight (provided that the whole copolymer is 100% by weight), and at least one polymerizable unsaturated compound in the molecule. Resin comprising a prepolymer (B) having a group and one or more carboxyl groups, and containing 0.1 to 100 parts by weight of the copolymer (A) per 100 parts by weight of the prepolymer (B) Composition. Embedded image (However, R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 8 carbon atoms, R ³ and R ³ ′ are a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, polyoxy An alkylene group, a polyoxyalkylene group having a terminal ether- or ester-substituted group, a polyalkylene polyamine group, a fatty acid group, or a polysiloxane group;
⁴ is a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, a polyoxyalkylene group, a polyoxyalkylene group having a terminal ether or ester substitution, a polyalkylene polyamine group, a fatty acid group, a polysiloxane group, a vinyl group. , A vinylalkylene group, a vinylhydroxyalkylene group, an acryloyloxyalkylene group or a methacryloyloxyalkylene group. m is an integer of 1 to 150. ) 2. Per 100 parts by weight of the prepolymer (B), 1 to 30 parts by weight of a photopolymerization initiator (C), 1 to 100 parts by weight of a reactive diluent (D), and epoxy resin (E) 2. The photosensitive resin composition according to claim 1, comprising 2 to 100 parts by weight. 3. A unit (a2) derived from an unsaturated monomer having a carboxyl group in a structural unit of the copolymer (A).
The photosensitive resin composition according to claim 1 or 2, wherein is obtained by a reaction between an unsaturated monomer having a hydroxyl group and an acid anhydride. 4. The prepolymer (B) according to claim 1, wherein the prepolymer (B) is obtained by reacting a reaction product of an epoxy compound and an unsaturated monocarboxylic acid with a polybasic acid anhydride. Item 2. The photosensitive resin composition according to item 1. 5. The carboxyl group formed by the reaction of the prepolymer (B) with a reaction product of an epoxy compound and an unsaturated monocarboxylic acid with a polybasic acid anhydride, and one epoxy group in the molecule. And a compound having one or more unsaturated groups.
The photosensitive resin composition according to any one of the above. 6. The unit (a3) derived from an unsaturated monomer in the structural unit of the copolymer (A) is a unit derived from an unsaturated monomer having a tertiary amino group. 6. The photosensitive resin composition according to any one of items 5 to 5. 7. The copolymer (A) according to claim 6, wherein
A photosensitive resin composition obtained by modifying a quaternary amino group to a quaternary ammonium salt.