JP2000321765A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition superior in cracking resistance, adhesion to copper, dryability to touch, heat resistance, resolution, flexibility, developability, moisture resistance, electric characteristics, and other necessary characteristics, high in reproductivity, reducible in cost, developable in alkali, and suitable for a buildup system multilayer print substrate. SOLUTION: This resin composition is obtained by reaction of (A) a novolak type epoxy compound and/or a glycol type epoxy compound with an unsaturated and/or saturated monobasic acid and further, a saturated or unsaturated polybasic acid anhydride, and it contains, further, (B) an epoxy resin, (C) a photopolymerization initiator, and (D) a photopolymerizable unsaturated compound and/or a solvent.

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, and more particularly, to a method of subjecting an exposed portion to heat treatment while irradiating an exposed portion with an active energy ray. , Excellent heat resistance, solvent resistance, acid resistance, adhesion with copper plating, flexibility and electrical properties, and build-up type multilayer printed wiring board,
The present invention relates to a photosensitive resin composition that can be used for a solder resist, a flexible printed wiring board, and the like, and is particularly suitable for a build-up type multilayer printed circuit board.

[0002]

2. Description of the Related Art In recent years, computers and electronic devices have been required to be smaller and more functional than ever.
In particular, printed circuit boards are required to have higher wiring density, finer circuits, and more layers. As one of the methods, development and commercialization of a build-up type multilayer printed circuit board are being promoted. This build-up type multilayer printed circuit board employs a method in which conductive circuits and interlayer insulating layers are alternately laminated, and wiring between layers is connected by via holes. Further, as a method of forming a via hole in a build-up type multilayer printed board, two methods, a method using a laser and a method using exposure and development using a photosensitive resin, are mainly studied.

[0003] The via hole forming method using a laser is capable of forming a fine pattern, but it takes a long time to perform a drilling operation, has low productivity, requires a cleaning step after drilling, and is expensive in dedicated equipment. The disadvantage is that the cost is high.

A method of forming a via hole using a photosensitive resin can be expected to be lower in cost than a method of forming a via hole by using a laser, because a hole can be collectively formed by exposure and development, and existing equipment can be used. As the developing method, a solvent developing method and a dilute alkaline developing method have been adopted.However, the former deteriorates the working environment due to the use of an organic solvent, or requires a closed system in order to improve them. The cost is high.

At present, as a photosensitive resin of a dilute alkali developing type, for example, a hydroxyl group formed by reacting acrylic acid as an unsaturated monobasic acid with a novolak type epoxy resin as disclosed in Japanese Patent Publication No. Novolak-type epoxy (meth) acrylate having a carboxyl group in the side chain obtained by reacting a saturated or unsaturated acid anhydride with carboxylic acid has been studied. However, when used as an interlayer insulating layer of a build-up type multilayer printed circuit board, Insufficient adhesion to copper plating due to insufficient adhesion to copper plating, low crack resistance due to hard cured coating, low development time or coating with low carboxyl group number in resin A curable and / or photosensitive resin composition for active energy rays that remains and has poor water resistance when the number of carboxyl groups is large. One of the ways to reduce touch drying due to the polymerizable unsaturated compound used for the purpose of improving coatability when used as a dist ink and to reduce costs is to improve productivity by improving photosensitivity and fine patterning. And other issues.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide crack resistance, adhesion to copper, dryness to the touch, heat resistance, resolution, flexibility, developability, water resistance, and electric resistance. Characteristic,
A photosensitive resin composition with excellent other required properties, high productivity and low cost, low solvent evaporation into the working environment, and particularly suitable for alkali-developed build-up type multilayer printed circuit boards To provide things.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have solved the above-mentioned conventional problems. That is, the present invention is obtained by reacting (A) a novolak-type epoxy compound and / or a glycol-based epoxy compound, an unsaturated monobasic acid and a saturated monobasic acid, and further reacting a saturated or unsaturated polybasic acid anhydride. Photosensitive resin,
A photosensitive resin composition comprising (B) an epoxy resin, (C) a photopolymerization initiator, and (D) a polymerizable unsaturated compound and / or a solvent.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The photosensitive resin (A) in the present invention is obtained by reacting an epoxy compound with an unsaturated monobasic acid and a saturated monobasic acid, and further reacting a saturated or unsaturated polybasic anhydride.

[0009] The epoxy compound is selected from a novolak type epoxy compound, a glycol type epoxy compound, or a combination thereof. The epoxy compound is preferably a compound in which the novolak-type epoxy compound is mixed at a ratio of 70 to 100% and the glycol-based epoxy compound at a ratio of 0 to 30%. As a novolak type epoxy compound,
An epoxy compound comprising a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, a dicyclopentadiene-phenol polyaddition type epoxy compound, or a combination thereof. Further, the novolak type epoxy compound may be halogenated. In addition, as long as the effect of the present invention is not impaired, a part of the novolak type epoxy compound is replaced with a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a phenol-cresol co-condensation type epoxy resin, a bisphenol A
Novolak type epoxy resin, bisphenol F Novolak type epoxy resin, triphenylol methane type epoxy resin, alkyl-substituted triphenylol methane type epoxy resin, tetraphenylol ethane type epoxy resin, etc. obtained by reacting epichlorohydrin with polyfunctional phenol. Epoxy compound, epoxy resin obtained by reacting epichlorohydrin with polyfunctional hydroxynaphthalenes, silicone-modified epoxy resin, ε-caprolactone-modified epoxy resin, glycidylamine type epoxy resin obtained by reacting epichlorohydrin with a primary or secondary amine, It can be replaced by a heterocyclic epoxy resin such as triglycidyl isocyanate.

Examples of the glycol-based epoxy compound include polyethylene glycol type, polypropylene glycol type, neopentyl glycol type and 1,6-hexane glycol type epoxy compounds. Two or more of these glycol epoxy compounds may be used in combination.

The unsaturated monobasic acid is a monobasic acid having one carboxyl group and one or more polymerizable unsaturated bonds, and specific examples include preferably using acrylic acid or methacrylic acid. For obtaining high active energy photocurability, acrylic acid is preferred. In addition, crotonic acid, cinnamic acid, sorbitan acid, acrylic acid dimer, monomethyl malate, monopropyl malate,
Monobutyl maleate, a carboxyl group-containing polyfunctional acrylate which is a reaction product of a polyfunctional acrylate or methacrylate having one hydroxyl group and one or more acryloyl groups and a dibasic acid among the polybasic anhydrides described below or Methacrylate. Two or more of these unsaturated monobasic acids may be used in combination.

The saturated monobasic acid is a saturated fatty acid represented by C _n H _{2n + 1} COOH, among which acetic acid, propionic acid,
Use of butyric acid and valeric acid is preferred. In addition, oxyacids that are saturated fatty acids having one or more hydroxyl groups in the molecule,
For example, glycolic acid, lactic acid, hydroacrylic acid, glyceric acid and the like can be mentioned. These saturated monobasic acids may be used alone or in combination of two or more.

In the photosensitive resin (A), the unsaturated monobasic acid and the saturated monobasic acid are reacted with each other in an amount of 0.8 to 1.1 equivalents based on 1.0 equivalent of the epoxy group of the epoxy compound, and 0.2 to 0.9 equivalent, preferably 0.3 to 0.8 equivalent of unsaturated monobasic acid and 0.1 to 0.9% of saturated monobasic acid.
The reaction is preferably performed at a ratio of 1 to 0.8 equivalent, preferably 0.2 to 0.7 equivalent. If the total of the unsaturated monobasic acid and the saturated monobasic acid is less than 0.8 equivalent, the storage stability will be poor, or there will be problems such as gelation during synthesis.
If it exceeds 1 equivalent, odor is generated or heat resistance is reduced. When the amount of the unsaturated monobasic acid used is less than 0.2 equivalent and the amount of the saturated monobasic acid exceeds 0.8 equivalent, sufficient active energy photocurability cannot be obtained, and the fine pattern is not obtained. If not obtained, and the amount of the unsaturated monobasic acid used exceeds 0.9 equivalents and the amount of the saturated monobasic acid used is less than 0.1 equivalents, the flexibility of the cured coating film is obtained. And the development time is long, which is not preferable.

The saturated or unsaturated polybasic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride,
Dibasic anhydrides such as hexahydrophthalic anhydride, endmethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyl Examples thereof include polybasic acid anhydrides such as tetracarboxylic anhydride, and particularly preferred is tetrahydrophthalic anhydride or hexahydrophthalic anhydride which has excellent electrolytic corrosion.

In the photosensitive resin (A), the saturated or unsaturated polybasic acid anhydride is reacted with an epoxy compound, an unsaturated monobasic acid and a saturated monobasic acid in an amount of 1.0 mol of a hydroxyl group of a reaction product obtained. On the other hand, the reaction is preferably carried out at a ratio of 0.2 to 0.9 mol, preferably 0.3 to 0.8 mol.
When the amount of the saturated or unsaturated polybasic acid anhydride is less than 0.2 mol, the solubility in dilute alkali and the heat resistance of the cured coating film are reduced, and the saturated or unsaturated polybasic acid anhydride is reduced. When the use amount exceeds 0.9 mol, the water resistance, alkali resistance, and electrical properties of the cured coating film deteriorate, and none of them is preferable.

The epoxy resin (B) has, for example, two or more epoxy groups in one molecule, and includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, and phenol novolak. Epoxy resin, cresol novolak epoxy resin, dicyclopentadiene-phenol novolak epoxy resin, phenol-cresol novolak co-condensation epoxy resin, bisphenol A novolak epoxy resin, bisphenol F novolak epoxy resin or their halogenated epoxy compounds Epichlorohydric to polyfunctional phenols such as triphenylol methane epoxy resin, alkyl-substituted triphenylol methane epoxy resin and tetraphenylol ethane epoxy resin An epoxy resin obtained by reacting an epoxy resin, an epoxy resin obtained by reacting a polyfunctional hydroxynaphthalene epichlorohydrin, a silicone-modified epoxy resin, an ε-caprolactone-modified epoxy resin, and a reaction obtained by reacting epichlorohydrin with a primary or secondary amine. Heterocyclic epoxy resins such as glycidylamine type epoxy resin and triglycidyl isocyanate are exemplified. One or more of these epoxy resins (B) may be used in combination.

The amount of the epoxy resin (B) used is 3 to 100 parts by weight, preferably 6 to 75 parts by weight, based on 100 parts by weight of the photosensitive resin (A). If the amount of the epoxy resin (B) is less than 3 parts by weight, the amount of the carboxyl group in the photosensitive resin (A) does not substantially satisfy the reaction amount, so that the water resistance, alkali resistance, and electric properties are undesirably reduced. . On the other hand, when the amount exceeds 100 parts by weight, a linear polymer having an unreacted epoxy group is generated, so that heat resistance and solvent resistance become insufficient, and neither is preferable.

To obtain a build-up type multilayer printed board using the photosensitive resin composition of the present invention, the photosensitive resin composition is applied to the substrate by, for example, a screen printing method, a roll coater method, or a curtain coater method. By heating, drying, irradiating with active energy, and photo-curing the necessary parts, dissolving the unexposed parts with a dilute alkaline aqueous solution,
After the coating film is obtained, a step of further heating and curing to form a coating film is included. Therefore, as a catalyst for accelerating the reaction between the photosensitive resin (A) and the epoxy resin (B) at the time of heat curing, an amine compound, an imidazole compound, a phenol compound,
A quaternary ammonium compound or a methylol compound may be added as long as the object of the present invention is not impaired.

Next, as the photopolymerization initiator (C), benzoin and its derivatives such as benzoin, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzyl ketal and its derivatives such as benzyl dimethyl ketal; acetophenone; , 2-dimethoxy-2-phenylacetophenone,
2,2-diethoxy-2-phenylacetophenone, 1,
Acetophenone such as 1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophyl) -2-morpholinopropan-1-one and derivatives thereof, 2-methylanthraquinone,
2-chloroanthraquinone, 2-ethylanthraquinone,
Anthraquinones and derivatives thereof such as 2-t-butylanthraquinone, thioxanthones and derivatives thereof such as thioxanthone, 2,4-dimethylthioxanthone and 2-chlorothioxane, and benzophenones and derivatives thereof such as benzophenone and N, N-dimethylaminobenzophenone. One or more of these photopolymerization initiators (C) may be used in combination.

Further, it is known that the use of various amine compounds in combination with these photopolymerization initiators, if necessary, promotes the photopolymerization initiation effect. In the present invention, it is also possible to use them in combination. it can.

The amount of the photopolymerization initiator (C) used is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the photosensitive resin (A).

The polymerizable unsaturated compound and / or the solvent (D) has curability to active energy rays and / or
Alternatively, it is used for the purpose of improving coatability when the photosensitive resin composition is used as a resist ink. As the polymerizable unsaturated compound, monomers having an active energy ray-curable property are preferable, and 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N-pyrrolidone, N-acryloyl morpholine,
N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, methoxy polyethylene glycol acrylate, ethoxy polyethylene glycol acrylate, melamine acrylate, phenoxyethyl acrylate, phenoxy Propyl acrylate, ethylene glycol diacrylate, dipropylene glycol diacrylate, polydipropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, glycerin diacrylate, isobornyl acrylate , Dicyclopentenyloxy Examples include ethyl acrylate and various methacrylates corresponding thereto. One or more of these polymerizable unsaturated compounds (D) may be used in combination.

On the other hand, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, carbitols such as ethyl cellosolve, butyl cellosolve, carbitol and butyl carbitol, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate and carbyl And tall acetate. These solvents may be used alone or in combination of two or more.

The polymerizable unsaturated compound or the solvent (D) is
It is used alone or as a mixture of two or more. The amount of the polymerizable unsaturated compound and / or the solvent (D) used is based on 100 parts by weight of the photosensitive resin (A).
It is 10 to 200 parts by weight, preferably 20 to 150 parts by weight. Above all, when the amount of the polymerizable unsaturated compound is less than 10 parts by weight, the photosensitivity is too low. On the other hand, when the amount is more than 200 parts by weight, the viscosity becomes too low when the photosensitive resin composition is used as a resist ink. The resistance as a coating film becomes insufficient.

In addition, when the photosensitive resin composition of the present invention is used as a liquid resist ink, if necessary, an inorganic filler such as silica, calcium carbonate, barium sulfate, clay, talc, and the like, phthalocyanine green ,
In addition to coloring pigments such as phthalocyanine blue, titanium oxide and carbon black, various additives such as defoamers and leveling agents, hydroquinone, resorcinol, catechol, pyroganol, hydroquinone monomethyl ether, t-
A polymerization inhibitor such as butyl catechol and phenothiazine may be used.

As an irradiation light source for curing the photosensitive resin composition of the present invention, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp and the like are suitable. Alternatively, a laser beam can be used.

[0027]

The present invention will be specifically described below with reference to examples and comparative examples. All parts and percentages are by weight unless otherwise specified.

Synthesis Example 1 Cresol novolac epoxy resin "Epototo YDCN-704" having an epoxy equivalent of 210 and a softening point of 80 ° C.
[Toto Kasei Co., Ltd.] 210 parts (1.00 equivalent (equivalent of epoxy group; the same applies hereinafter)) (100% of novolak type epoxy compound, 0% of glycol type epoxy compound)
%), 50 parts (0.7 equivalent) of acrylic acid, 18 parts (0.3 equivalent) of acetic acid in 139 parts of toluene, 0.5 part of dimethylbenzylamine as a catalyst, and 0.1 part of hydroquinone as a polymerization inhibitor And 278 parts of a reaction product (epoxy acrylate) obtained by the reaction, and 46 parts of tetrahydrophthalic anhydride (0.3 mol (1.0 mol of hydroxyl group of the reaction product)).
Values for moles. The same applies to the following) to obtain a photosensitive resin having an acid value of 52 mgKOH / g in solid content.

Synthesis Example 2 Cresol novolak type epoxy resin having an epoxy equivalent of 210 and a softening point of 80 ° C. “Sumi Epoxy ESCN-220”
HH "[manufactured by Sumitomo Chemical Co., Ltd.] 195 parts (0.93
1,6-hexanediol diglycidyl ether “Denacol EX-212” having an epoxy equivalent of 150 and an epoxy equivalent of 150
[Nagase Chemical Industry Co., Ltd.] 11 parts (0.07 equivalent)
(95% of a novolak type epoxy compound, 5% of a glycol type epoxy compound), 50 parts (0.7 equivalent) of acrylic acid, and 18 parts (0.3 equivalent) of acetic acid in 163 parts of toluene. Using 5 parts of hydroquinone as a polymerization inhibitor and 0.1 part of a polymerization inhibitor, 274 parts of an epoxy acrylate obtained by the reaction were reacted with 106 parts (0.7 mol) of tetrahydrophthalic anhydride, and the solid acid value was 103 mg KOH. / G of a photosensitive resin.

Synthesis Example 3 150 parts (0.80 equivalent) of a phenol novolak type epoxy resin "Epiclon N-770" (manufactured by Dainippon Ink and Chemicals, Inc.) having an epoxy equivalent of 188 and a softening point of 70 ° C.
30 parts (0.20 equivalents) of 1,6-hexanediol diglycidyl ether "Denacol EX-212" (manufactured by Nagase Kasei Kogyo Co., Ltd.) having an epoxy equivalent of 150 (83% of novolak epoxy compound, glycol epoxy Compound 17%), 29 parts of acrylic acid (0.4 equivalent),
245 parts of an epoxy acrylate obtained by reacting 36 parts (0.6 equivalent) of acetic acid in 125 parts of toluene using 0.5 part of triphenylphosphine as a catalyst and 0.1 part of hydroquinone as a polymerization inhibitor, This was reacted with 46 parts (0.3 mol) of tetrahydrophthalic anhydride to obtain a photosensitive resin having a solid content acid value of 58 mgKOH / g.

Synthesis Example 4 Cresol novolak epoxy resin "Epototo YDCN-704" having an epoxy equivalent of 210 and a softening point of 80 ° C.
[Toto Kasei Co., Ltd.] 126 parts (0.60 equivalents) of dicyclopentadiene-phenol novolak type epoxy resin having a softening point of 95 ° C. “Epiclon HP-7200H”
[Dainippon Ink Chemical Industry Co., Ltd.] 84 parts (0.30
Equivalent) and an epoxy equivalent of 470, polypropylene glycol diglycidyl ether "Denacol EX-931"
[Nagase Kasei Kogyo Co., Ltd.] 47 parts (0.10 equivalent)
(80% of novolak type epoxy compound, 20% of glycol type epoxy compound), 50 parts of acrylic acid (0.7%
Epoxy acrylate obtained by reacting 18 parts (0.3 equivalent) of acetic acid and 150 parts of toluene with 0.5 part of trimethylbenzylammonium chloride as a catalyst and 0.1 part of hydroquinone as a polymerization inhibitor in 150 parts of toluene. 304 parts and tetrahydrophthalic anhydride 46 parts (0.
3 mol) and an acid value of the solid content of 48 mgKOH /
g of the photosensitive resin was obtained.

Synthesis Example 5 Cresol novolak type epoxy resin having an epoxy equivalent of 210 and a softening point of 80 ° C. “Sumi Epoxy ESCN-220”
HH "[manufactured by Sumitomo Chemical Co., Ltd.] 183 parts (0.87
Equivalent) and an epoxy equivalent of 470, polypropylene glycol diglycidyl ether "Denacol EX-931"
[Nagase Chemical Industries Ltd.] 61 parts (0.13 equivalent)
(75% of novolak type epoxy compound, 25% of glycol type epoxy compound), 50 parts of acrylic acid (0.7%)
Epoxy acrylate obtained by reacting 18 parts (0.3 equivalent) of acetic acid with 153 parts of toluene using 0.5 part of trimethylbenzylammonium chloride as a catalyst and 0.1 part of hydroquinone as a polymerization inhibitor. 312 parts and 46 parts of tetrahydrophthalic anhydride (0.
3 mol) and the acid value of the solid was 47 mg KOH /
g of the photosensitive resin was obtained.

Synthesis Example 6 200 parts (0.95 equivalent) of a cresol novolac epoxy resin "Epiclon N-680" (manufactured by Dainippon Ink and Chemicals, Inc.) having an epoxy equivalent of 210 and a softening point of 80 ° C.
And 24 parts (0.05 equivalent) of polypropylene glycol diglycidyl ether “Denacol EX-931” (manufactured by Nagase Kasei Kogyo Co., Ltd.) having an epoxy equivalent of 470 (89% of the novolak epoxy compound and 11% of the glycol epoxy compound) ), 50 parts of acrylic acid (0.7 equivalent),
Epoxy acrylate 291 obtained by reacting 18 parts (0.3 equivalent) of acetic acid in 138 parts of toluene using 0.5 part of trimethylbenzylammonium chloride as a catalyst and 0.1 part of hydroquinone as a polymerization inhibitor.
Parts and 30 parts of tetrahydrophthalic anhydride (0.2 mol)
To obtain a photosensitive resin having a solid content acid value of 35 mgKOH / g.

Synthesis Example 7 Dicyclopentadiene-phenol novolak epoxy resin “Epiclon HP-7200H” having an epoxy equivalent of 280 and a softening point of 95 ° C. [manufactured by Dainippon Ink and Chemicals, Inc.] 252 parts (0.90 equivalent) And an epoxy equivalent of 138, neopentyl glycol diglycidyl ether "Denacol EX-211" [Nagase Kasei Kogyo Co., Ltd.] 14
Parts (0.10 equivalents) (9 novolak epoxy compounds
5%, 5% of a glycol-based epoxy compound), 50 parts (0.7 equivalent) of acrylic acid, 21 parts (0.3 equivalent) of butyric acid in 202 parts of toluene, 0.5 part of triethylamine as a catalyst, a polymerization inhibitor Acrylate 343 obtained by reacting with 0.1 part of hydroquinone
Were reacted with 122 parts (0.8 mol) of tetrahydrophthalic anhydride to obtain a photosensitive resin having a solid content acid value of 97 mgKOH / g.

Synthesis Example 8 Cresol novolak type epoxy resin having an epoxy equivalent of 210 and a softening point of 80 ° C. “Sumi Epoxy ESCN-220”
HH "[manufactured by Sumitomo Chemical Co., Ltd.] 147 parts (0.70
Equivalent) and 56 parts (0.20 equivalent) of dicyclopentadiene-phenol novolak type epoxy resin “Epiclon HP-7200H” (manufactured by Dainippon Ink and Chemicals, Inc.) having an epoxy equivalent of 280 and a softening point of 95 ° C. 150 1,6-hexanediol diglycidyl ether "Denacol EX-212" [Nagase Chemical Industry Co., Ltd.]
15 parts (0.10 equivalent) (93% of novolak type epoxy compound, 7% of glycol type epoxy compound)
%), 36 parts (0.5 equivalent) of acrylic acid and 30 parts (0.5 equivalent) of acetic acid in 180 parts of toluene, 0.5 part of trimethylbenzylammonium chloride as a catalyst, and 0.1 part of hydroquinone as a polymerization inhibitor. 284 parts of an epoxy acrylate obtained by the above reaction and 137 parts (0.9 mol) of tetrahydrophthalic anhydride were reacted to obtain a photosensitive resin having a solid content acid value of 120 mgKOH / g.

Synthesis Example 9 Cresol novolak epoxy resin "Epototo YDCN-704" having an epoxy equivalent of 210 and a softening point of 80 ° C.
[Toto Kasei Co., Ltd.] 126 parts (0.60 equivalents) and a phenol novolak type epoxy resin “Epiclon N-770” having a softening point of 70 ° C. [Dainippon Ink and Chemicals Co., Ltd.] 56 parts (0 .30 equivalents) and an epoxy equivalent of 165, polypropylene glycol diglycidyl ether “Denacol EX-911” [manufactured by Nagase Kasei Kogyo Co., Ltd.] 15
Parts (0.10 equivalents) (9 novolak epoxy compounds
2%, 8% of a glycol-based epoxy compound), 22 parts (0.3 equivalent) of acrylic acid and 42 parts (0.7 equivalent) of acetic acid in 132 parts of toluene, 0.5 part of triphenylphosphine as a catalyst, and polymerization Hydroquinone is used as an inhibitor.
Epoxy acrylate 2 obtained by reacting with 1 part
63 parts and 46 parts (0.3 mol) of tetrahydrophthalic anhydride were reacted to obtain a photosensitive resin having a solid content acid value of 55 mgKOH / g.

Synthesis Example 10 Cresol novolac epoxy resin “Epototo YDCN-704” having an epoxy equivalent of 210 and a softening point of 80 ° C.
[Toto Kasei Co., Ltd.] 200 parts (0.95 equivalents) and an epoxy equivalent of 470 polypropylene glycol diglycidyl ether "Denacol EX-931" [Nagase Kasei Kogyo Co., Ltd.] 24 parts (0.05 equivalents) ) (89% of novolak type epoxy compound, 11% of glycol type epoxy compound), 65 parts (0.9 equivalent) of acrylic acid and 7 parts (0.1 equivalent) of acetic acid in 146 parts of toluene, trimethylbenzyl as a catalyst Ammonium chloride 0.5
Parts, using 0.1 part of hydroquinone as a polymerization inhibitor,
295 parts of an epoxy acrylate obtained by the reaction,
This was reacted with 46 parts (0.3 mol) of tetrahydrophthalic anhydride to obtain a photosensitive resin having a solid acid value of 49 mgKOH / g.

Synthesis Example 11 Cresol novolak type epoxy resin having an epoxy equivalent of 210 and a softening point of 80 ° C. “Sumi Epoxy ESCN-220”
HH "[manufactured by Sumitomo Chemical Co., Ltd.] 200 parts (0.90
1,6-hexanediol diglycidyl ether “Denacol EX-212” having an epoxy equivalent of 150 and an epoxy equivalent of 150
[Nagase Chemical Industries Ltd.] 15 parts (0.10 equivalent)
(93% of novolak type epoxy compound, 7% of glycol type epoxy compound), 50 parts (0.7 equivalent) of acrylic acid, and 12 parts (0.2 equivalent) of acetic acid in 134 parts of toluene, triphenylphosphine was used as a catalyst. Using 0.5 part, 0.1 part of hydroquinone as a polymerization inhibitor, and reacting 266 parts of an epoxy acrylate obtained by the reaction with 46 parts (0.3 mol) of tetrahydrophthalic anhydride,
A photosensitive resin having an acid value of 54 mgKOH / g in solid content was obtained.

Synthesis Example 12 Cresol novolak type epoxy resin having an epoxy equivalent of 210 and a softening point of 80 ° C. “Sumi Epoxy ESCN-220”
HH "[manufactured by Sumitomo Chemical Co., Ltd.] 200 parts (0.90
1,6-hexanediol diglycidyl ether “Denacol EX-212” having an epoxy equivalent of 150 and an epoxy equivalent of 150
[Nagase Chemical Industries Ltd.] 15 parts (0.10 equivalent)
(93% of novolak type epoxy compound, 7% of glycol type epoxy compound), 50 parts (0.7 equivalent) of acrylic acid and 24 parts (0.4 equivalent) of acetic acid in 134 parts of toluene, trimethylbenzylammonium as a catalyst 0.5 part of chloride and hydroquinone as a polymerization inhibitor in 0.1 part.
Epoxy acrylate 2 obtained by reacting with 1 part
78 parts were reacted with 46 parts (0.3 mol) of tetrahydrophthalic anhydride to obtain a photosensitive resin having a solid content acid value of 55 mgKOH / g.

Synthesis Example 13 Cresol novolak epoxy resin "Epototo YDCN-704" having an epoxy equivalent of 210 and a softening point of 80 ° C.
[Toto Kasei Co., Ltd.] 105 parts (0.50 equivalent) and phenol novolac epoxy resin "Epiclon N-770" having a softening point of 70 ° C. [Dainippon Ink and Chemicals Co., Ltd.] 38 parts (0 Dicyclopentadiene-phenol novolak type epoxy resin “Epiclon HP-7200H” having an epoxy equivalent of 280 and a softening point of 95 ° C.
[Dainippon Ink Chemical Industry Co., Ltd.] 56 parts (0.20
1,6-hexanediol diglycidyl ether “Denacol EX-212” having an epoxy equivalent of 150 and an epoxy equivalent of 150
[Nagase Chemical Industries Ltd.] 15 parts (0.10 equivalent)
(93% of novolak type epoxy compound, 7% of glycol type epoxy compound), 29 parts (0.4 equivalent) of acrylic acid, 36 parts (0.6 equivalent) of acetic acid in 139 parts of toluene, dimethylbenzylamine as a catalyst Using 0.5 part, 0.1 part of hydroquinone as a polymerization inhibitor, and reacting 278 parts of an epoxy acrylate obtained by the reaction with 46 parts (0.3 mol) of tetrahydrophthalic anhydride,
A photosensitive resin having a solid content acid value of 52 mgKOH / g was obtained.

Synthesis Example 14 A cresol novolak type epoxy resin having an epoxy equivalent of 210 and a softening point of 80 ° C. “Sumi Epoxy ESCN-220”
HH "[manufactured by Sumitomo Chemical Co., Ltd.] 210 parts (1.0 equivalent), 50 parts (0.7 equivalent) of acrylic acid, 18 parts (0.3 equivalent) of acetic acid in 152 parts of toluene as a catalyst Using 0.5 part of triethylamine and 0.1 part of hydroquinone as a polymerization inhibitor, 278 parts of an epoxy acrylate obtained by the reaction are reacted with 76 parts (0.5 mol) of tetrahydrophthalic anhydride to obtain a solid acid. Price is 79mgK
An OH / g photosensitive resin was obtained.

Synthesis Example 15 A phenol novolak type epoxy resin “Epiclon N-770” having an epoxy equivalent of 188 and a softening point of 70 ° C. [manufactured by Dainippon Ink and Chemicals, Inc.] 188 parts (1.0 equivalent),
29 parts (0.4 equivalents) of acrylic acid, 41 parts (0.55 equivalents) of propionic acid and 4 parts (0.05 equivalents) of butyric acid in 131 parts of toluene, 0.5 parts of dimethylbenzylamine as a catalyst, polymerization inhibition Using 0.1 part of methylhydroquinone as an agent, 262 parts of an epoxy acrylate obtained by the reaction and 46 parts of tetrahydrophthalic anhydride (0.
3 mol), and the solid content acid value is 55 mg KOH /
g of the photosensitive resin was obtained.

Synthesis Example 16 Dicyclopentadiene-phenol novolak type epoxy resin “Epiclon HP-7200H” having an epoxy equivalent of 280 and a softening point of 95 ° C. [manufactured by Dainippon Ink and Chemicals, Inc.] 280 parts (1.00 equivalent) 58 parts (0.80 equivalents) of acrylic acid and 12 parts (0.20 equivalents) of acetic acid in 195 parts of toluene, 0.5 part of trimethylbenzylammonium chloride as a catalyst, and 0.1 part of methylhydroquinone as a polymerization inhibitor. Using 350 parts of epoxy acrylate obtained by the reaction, 106 parts (0.7 mol) of tetrahydrophthalic anhydride were reacted to obtain a photosensitive resin having a solid content acid value of 86 mgKOH / g.

Synthesis Example 17 Cresol novolak epoxy resin "Epototo YDCN-704" having an epoxy equivalent of 210 and a softening point of 80 ° C.
[Toto Kasei Co., Ltd.] 132 parts (0.70 equivalents), epoxy equivalent 280, softening point 95 ° C. dicyclopentadiene-phenol novolak type epoxy resin “Epiclon HP-7200H” [Dainippon Ink Chemical Industry Co., Ltd. 280 parts (0.30 equivalents), 22 parts (0.30 equivalents) of acrylic acid, 42 parts (0.70 equivalents) of acetic acid in 146 parts of toluene and 0.5 parts of triethylamine as a catalyst.
Parts, using 0.1 part of hydroquinone as a polymerization inhibitor,
295 parts of an epoxy acrylate obtained by the reaction,
This was reacted with 46 parts (0.30 mol) of tetrahydrophthalic anhydride to obtain a photosensitive resin having a solid acid value of 49 mgKOH / g.

Synthesis Example 18 Phenol novolak type epoxy resin “Epiclon N-770” having a softening point of 188 and a softening point of 70 ° C. (manufactured by Dainippon Ink and Chemicals, Inc.) 132 parts (0.7 equivalent) and an epoxy equivalent of 280 , A dicyclopentadiene-phenol novolak type epoxy resin having a softening point of 95 ° C. “Epiclon HP-7200H” [manufactured by Dainippon Ink and Chemicals, Inc.], 84 parts (0.30 equivalents), and 65 parts of acrylic acid (0. 9 equivalents), 6 parts of acetic acid (0.1 equivalent)
In 40 parts, 0.5 part of triethylamine was used as a catalyst, and 0.1 part of hydroquinone was used as a polymerization inhibitor, 281 parts of an epoxy acrylate obtained by a reaction, and 46 parts (0.3 mol) of tetrahydrophthalic anhydride were used. Was reacted to obtain a photosensitive resin having a solid content acid value of 51 mgKOH / g.

Synthesis Example 19 Cresol novolak type epoxy resin having an epoxy equivalent of 210 and a softening point of 80 ° C. “Sumi Epoxy ESCN-220”
HH "[manufactured by Sumitomo Chemical Co., Ltd.] 105 parts (0.50
Phenol novolak type epoxy resin “Epiclon N-770” having an epoxy equivalent of 188 and a softening point of 70 ° C.
[Manufactured by Dainippon Ink and Chemicals, Inc.] 56 parts (0.3 equivalent), a dicyclopentadiene-phenol novolak type epoxy resin having an epoxy equivalent of 280 and a softening point of 95 ° C. “Epiclon HP-7200H” [Dainippon Ink Chemical Industrial Co., Ltd.] 56 parts (0.20 equivalent), acrylic acid 50
Parts (0.7 equivalents) and 18 parts (0.3 equivalents) of acetic acid in 136 parts of toluene using 0.5 parts of trimethylbenzylammonium chloride as a catalyst and 0.1 parts of methylhydroquinone as a polymerization inhibitor. 286 parts of the epoxy acrylate obtained above and 30 parts (0.2 mol) of tetrahydrophthalic anhydride were reacted to obtain a solid acid value of 3
6 mgKOH / g of a photosensitive resin was obtained.

Synthesis Example 20 Cresol novolak type epoxy resin “Epototo YDCN-704” having an epoxy equivalent of 210 and a softening point of 80 ° C.
[Toto Kasei Co., Ltd.] 210 parts (1.0 equivalent), 50 parts (0.7 equivalent) of acrylic acid, 18 parts (0.3 equivalent) of acetic acid in 178 parts of toluene, trimethylbenzylammonium as a catalyst Using 0.5 part of chloride and 0.1 part of methylhydroquinone as a polymerization inhibitor, 278 parts of an epoxy acrylate obtained by the reaction are reacted with 137 parts (0.9 mol) of tetrahydrophthalic anhydride,
A photosensitive resin having a solid content acid value of 122 mgKOH / g was obtained.

Synthesis Example 21 Cresol novolak type epoxy resin having an epoxy equivalent of 210 and a softening point of 80 ° C. “Sumi Epoxy ESCN-220”
HH "[manufactured by Sumitomo Chemical Co., Ltd.] 210 parts (1.00
Equivalent) and 150 equivalents of polypropylene glycol diglycidyl ether “Denacol EX-810”
[Nagase Chemical Industry Co., Ltd.] 60 parts (0.40 equivalent)
(68% of novolak type epoxy compound and 32% of glycol type epoxy compound) and 72 parts of acrylic acid (1.0%)
0 parts by weight) in 121 parts of toluene, 0.5 part of triphenylphosphine as a catalyst and 0.1 part of hydroquinone as a polymerization inhibitor, and 282 parts of an epoxy acrylate obtained by a reaction (solid acid value is 0 mgKOH). / G)
Was obtained.

Synthesis Example 22 188 parts (1.00 equivalent) of bisphenol-A type epoxy resin "Epicoat 828" (manufactured by Yuka Shell Epoxy Co., Ltd.) having an epoxy equivalent of 188 (0% of novolak type epoxy compound, glycol type 0% epoxy compound, 100% bisphenol-A type epoxy compound) and 72 parts (1.00 equivalent) of acrylic acid in 177 parts of toluene, 0.5 part of triphenylphosphine as a catalyst, and hydroquinone as a polymerization inhibitor Is reacted with 260 parts of an epoxy acrylate obtained by the reaction and 136 parts (1.0 mol) of tetrahydrophthalic anhydride to obtain a photosensitive resin having a solid content acid value of 136 mgKOH / g. Was.

Synthesis Example 23 Cresol novolak type epoxy resin having an epoxy equivalent of 210 and a softening point of 80 ° C. “Sumi Epoxy ESCN-220”
HH "[manufactured by Sumitomo Chemical Co., Ltd.] 210 parts (1.00
(Equivalent), (100% of novolak type epoxy compound, 0% of glycol type epoxy compound) and 60 parts of acetic acid (1.
Epoxide acetic acid adduct 275 obtained by reacting 0.5 parts of triethylamine as a catalyst with 46 parts (0.95 mol) of tetrahydrophthalic anhydride in 180 parts of toluene, The acid value is 127m
gKOH / g of the photosensitive resin was obtained.

Example 1 To 100 parts of the resin obtained in Synthesis Example 1, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-1) was produced.

70 parts of 1,3,5-triglycidyl isocyanurate "TEPIC" (manufactured by Nissan Chemical Industries, Ltd.) having an epoxy equivalent of 99, and butyl cellosolve acetate 3
100 parts of a curing agent (B-1) containing 0 parts was prepared.

Next, after mixing 200 parts of the main agent (A-1) and 23 parts of the curing agent (B-1) (hereinafter, the mixture is referred to as “the main agent (A-1) and the curing agent (B-2)”). Mixture)),
This mixture is applied to the entire surface of a printed circuit board having a copper through hole on which a circuit is formed in advance by a screen printing method so as to have a thickness of 30 to 40 μm, dried at 80 ° C. for 20 minutes, cooled to room temperature, and dried and applied. The film (1-a) was obtained. A pattern film was set on this coating film, and exposed for 60 seconds using a parallel ultra-high pressure mercury lamp exposure device manufactured by Oak Manufacturing Co., Ltd., and then developed for 60 seconds by spraying using a 1% aqueous solution of sodium carbonate at a liquid temperature of 30 ° C. Then use a hot air drier 1
Heat treatment was performed at 50 ° C. for 30 minutes to obtain a printed wiring board on which a photo via hole pattern was formed.

The interlayer electric insulating coating film of the printed wiring board having the photo via hole formed thereon was washed with potassium hydroxide at pH = 1.
The surface was roughened with an alkaline potassium permanganate solution at 60 to 80 ° C. adjusted to 3, neutralized the remaining alkali, washed with water and dried.

A conditioner treatment, microetching, pickling, catalysis, and accelerator treatment are sequentially performed on the printed wiring board having the surface-roughened interlayer insulating coating film in the same manner as in the pattern forming step by the semi-additive method, and the electroless copper Plating was performed, and a thin copper plating having a thickness of 0.3 μm was applied on the roughened interlayer electric insulating coating film.

The printed wiring board subjected to electroless copper plating is placed in a plating tank containing a copper plating bath to serve as a cathode, and an anode is placed on both sides of the printed wiring board, and a current is applied to the printed wiring board to perform electrolytic copper plating with a thickness of 18 μm. The specimen (1-b) was washed with water and dried to give a copper plating on one side.

The above main agent (A-1) and curing agent (B-1)
Is applied to the entire surface by a screen printing method so as to have a thickness of 30 to 40 μm on a printed circuit board.
After drying at 20 ° C. for 20 minutes, the diameter was 10 μm, 20 μm,
0 μm,. . . , 230 μm, 240 μm, 250 μm
After exposure for 60 seconds with a parallel ultra-high pressure mercury lamp exposure device manufactured by Oak Manufacturing Co., Ltd. through a mask provided with holes having a diameter which expands in a range of 10 to 250 μm at intervals of 10 μm as described above, the liquid temperature of 30 ° C. 6% aqueous solution of sodium carbonate
After performing development for 0 second, and performing heat treatment at 150 ° C. for 30 minutes using a hot air drier, a test piece (1-
c) was obtained.

Separately, a mixture of the main agent (A-1) and the curing agent (B-2) is coated on a 0.8 mm-thick steel plate whose surface is previously polished with No. 280 abrasive paper according to JIS K5400. After applying the whole surface by a screen printing method so as to have a thickness of 40 μm and drying it at 80 ° C. for 20 minutes, it was exposed for 60 seconds using a parallel ultra-high pressure mercury lamp exposure device manufactured by Oak Manufacturing Co., Ltd., and heated to 150 ° C. using a hot air drier. For 30 minutes to obtain a test specimen (1-d) for a flexibility test.

In addition, the main agent (A-1) and the curing agent (B-
Developable specimen (1-e) obtained by applying the mixture of 2) to the entire surface of the copper-clad substrate by screen printing so as to have a thickness of 30 to 40 μm and drying at 80 ° C. for 20 minutes, Oak Manufacturing Co., Ltd. Exposure was performed for 60 seconds using a parallel ultra-high pressure mercury lamp exposure apparatus manufactured by Co., Ltd., and heat treatment was performed at 150 ° C. for 30 minutes using a hot air drier, and the resulting coating film was prepared in the same manner as in the method of obtaining the specimen (1-b). After performing surface roughening and plating, the water-resistant specimen (1-
f) was obtained.

According to the evaluation test method shown below, the dryness to the touch is (1-a), the peel strength of the copper foil and the solder heat resistance are (1-b), and the resolution is (1-c). The flexibility is (1-
d) Developability is test sample (1-e) and water resistance is (1-e)
The measurement was performed using f), and the results are shown in Table 1.

[Evaluation Test Method] Dryness to the touch: A polyethylene film was adhered to the test sample (1-a), and the adhesion to the film when pressed with a finger was observed. ：: Peel cleanly. ×: Does not peel.

Peel strength: Using the test piece (1-b) having one surface coated with copper, the tip of the peeled copper foil is gripped with a gripper in accordance with JIS C6481, and the tensile direction is perpendicular to the copper foil surface. The copper foil was peeled in a certain direction, and the lowest value at this time was defined as the peel strength of the copper foil.

Solder heat resistance: Using the test piece (1-b),
According to IS C6481, one side of the copper foil faces down,
The whole surface was floated so as to be immersed in the solder, floated three times in a solder bath at 260 ° C. for 10 seconds, taken out, and observed for the occurrence of abnormalities such as swelling or peeling of the copper foil surface and the interlayer insulating layer surface and cracks. .

：: No change in appearance. ×: Appearance change (whitening or cracking of insulating layer surface; peeling or swelling of copper foil surface).

Resolution: Using the specimen (1-c), the photo via hole was observed with an SEM, and the diameter of the via hole having the smallest developed diameter was defined as the resolution.

Flexibility test: Using the specimen (1-d),
Using an Erichsen tester stipulated in JIS B 7729 A method according to IS K5400, a hard sphere is extruded from the back surface of the test piece, and the extruding distance until cracking and peeling of the coating film occurs when the test piece is deformed is measured. did.

Developability: 1% of test sample (1-e) at 30 ° C.
Spray pressure of 2.0kgf / mm with sodium carbonate aqueous solution
^Using the developing machine No. ² , the presence or absence of the coating film after the development was observed.

A: No coating film was visually observed after a developing time of 40 seconds. ：: No coating film was visually observed after a development time of 60 seconds. ×: A residual film was visually observed after a development time of 60 seconds.

Water resistance: After the specimen (1-f) was allowed to stand in boiling water at 100 ° C. for 24 hours, swelling, whitening and peeling of the coating film were observed.

○: No change in appearance. ×: Appearance change (whitening or cracking of insulating layer surface; peeling or swelling of copper foil surface).

Example 2 To 100 parts of the resin obtained in Synthesis Example 2, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-2) was produced.

A cresol novolak type epoxy resin “Epiclon N-68” having an epoxy equivalent of 210 and a softening point of 80 ° C.
No. 0 "(manufactured by Dainippon Ink & Chemicals, Inc.) and 30 parts of butyl cellosolve acetate (B)
-2) was prepared in an amount of 100 parts.

Next, using a mixture obtained by mixing 200 parts of the main agent (A-2) and 46 parts of the curing agent (B-2), the specimens (2-a, 2-b, -C, 2-
d, 2-e, 2-f) were prepared, and the results of measurement according to the evaluation test method shown in Example 1 are shown in Table 1.

Example 3 To 100 parts of the resin obtained in Synthesis Example 3, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-3) was produced.

Next, a sample (3-a) was prepared in the same manner as in Example 1 by using a mixture obtained by mixing 200 parts of the base material (A-3) and 46 parts of the curing agent (B-2) used in Example 1. , 3-
b, 3-c, 3-d, 3-e, 3-f) were prepared and measured according to the evaluation test method shown in Example 1.
Shown in

Example 4 Based on 100 parts of the resin obtained in Synthesis Example 4, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-4) was produced.

Next, a mixture of 200 parts of the base material (A-4) and 20 parts of the curing agent (B-2) used in Example 1 was used. , 4-
b, 4-c, 4-d, 4-e, 4-f) were prepared and measured according to the evaluation test method shown in Example 1.
Shown in

Example 5 To 100 parts of the resin obtained in Synthesis Example 5, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-5) was produced.

Then, a mixture of 200 parts of the main agent (A-5) and 21 parts of the curing agent (B-2) used in Example 1 was used. , 5-
b, 5-c, 5-d, 5-e, 5-f) were prepared and measured according to the evaluation test method shown in Example 1.
Shown in

Example 6 To 100 parts of the resin obtained in Synthesis Example 6, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-6) was prepared.

Next, a mixture of 200 parts of the base material (A-6) and 16 parts of the curing agent (B-2) used in Example 1 was used in the same manner as in Example 1 to obtain a sample (6-a). , 6-
b, 6-c, 6-d, 6-e, 6-f) were prepared and measured according to the evaluation test method shown in Example 1.
Shown in

Example 7 To 100 parts of the resin obtained in Synthesis Example 7, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-7) was produced.

Next, a mixture of 200 parts of the base material (A-7) and 20 parts of the curing agent (B-1) used in Example 1 was used. , 7-
b, 7-c, 7-d, 7-e, 7-f) were prepared and measured according to the evaluation test method shown in Example 1 and the results are shown in Table 1.
Shown in

Example 8 Based on 100 parts of the resin obtained in Synthesis Example 8, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-8) was produced.

Then, a mixture of 200 parts of the base material (A-8) and 54 parts of the curing agent (B-2) used in Example 1 was used, and the specimen (8-a , 8-
b, 8-c, 8-d, 8-e, 8-f) were prepared and measured according to the evaluation test method shown in Example 1.
Shown in

Example 9 To 100 parts of the resin obtained in Synthesis Example 9, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-9) was prepared.

Then, a mixture of 200 parts of the base material (A-9) and 24 parts of the curing agent (B-2) used in Example 1 was used. , 9-
b, 9-c, 9-d, 9-e, 9-f) were prepared and measured according to the evaluation test method shown in Example 1.
Shown in

Example 10 To 100 parts of the resin obtained in Synthesis Example 10, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-10) was produced.

Next, a mixture of 200 parts of the base material (A-10) and 23 parts of the curing agent (B-2) used in Example 1 was used. , 1
0-b, 10-c, 10-d, 10-e, 10-f) were prepared, and the results of measurement according to the evaluation test method shown in Example 1 are shown in Table 1.

Example 11 To 100 parts of the resin obtained in Synthesis Example 11, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-11) was produced.

Next, a mixture of 200 parts of the main agent (A-11) and 24 parts of the curing agent (B-2) used in Example 1 was used. , 1
1-b, 11-c, 11-d, 11-e, 11-f) were prepared, and the results of measurement according to the evaluation test method shown in Example 1 are shown in Table 1.

Example 12 To 100 parts of the resin obtained in Synthesis Example 12, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-12) was produced.

Then, a mixture of 200 parts of the base material (A-12) and 11 parts of the curing agent (B-1) used in Example 1 was used, and the specimen (12-a , 1
2-b, 12-c, 12-d, 12-e, 12-f) were prepared, and the results of measurement according to the evaluation test method shown in Example 1 are shown in Table 1.

Example 13 To 100 parts of the resin obtained in Synthesis Example 13, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-13) was prepared.

Then, a mixture of 200 parts of the base material (A-13) and 23 parts of the curing agent (B-2) used in Example 1 was used, and the specimen (13-a , 1
3-b, 13-c, 13-d, 13-e, 13-f) were prepared and measured according to the evaluation test method shown in Example 1 and the results are shown in Table 1.

Example 14 To 100 parts of the resin obtained in Synthesis Example 14, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-14) was produced.

Next, a mixture of 200 parts of the base material (A-14) and 17 parts of the curing agent (B-1) used in Example 1 was used, and the specimen (14-a , 1
4-b, 14-c, 14-d, 14-e, 14-f) were prepared, and the results of measurement according to the evaluation test method shown in Example 1 are shown in Table 2.

Example 15 To 100 parts of the resin obtained in Synthesis Example 15, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-15) was prepared.

A cresol novolak type epoxy resin “Epiclon N-68” having an epoxy equivalent of 210 and a softening point of 80 ° C.
No. 0 "(manufactured by Dainippon Ink & Chemicals, Inc.) and 30 parts of butyl cellosolve acetate (B)
-2) was prepared in an amount of 100 parts.

Next, a mixture obtained by mixing 200 parts of the base material (A-15) and 24 parts of the curing agent (B-2) was used.
Specimens (15-a, 15-b, 15-
c, 15-d, 15-e and 15-f) were prepared, and the results of measurement according to the evaluation test method shown in Example 1 are shown in Table 2.

Example 16 To 100 parts of the resin obtained in Synthesis Example 16, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-16) was produced.

Next, using a mixture of 200 parts of the base material (A-16) and 39 parts of the curing agent (B-2) used in Example 1, a sample (16-a , 1
6-b, 16-c, 16-d, 16-e, 16-f) were prepared, and the results of measurement according to the evaluation test method shown in Example 1 are shown in Table 2.

Example 17 To 100 parts of the resin obtained in Synthesis Example 17, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-17) was prepared.

Then, a mixture of 200 parts of the base material (A-17) and 23 parts of the curing agent (B-2) used in Example 1 was used in the same manner as in Example 1 to obtain a sample (17-a). , 1
7-b, 17-c, 17-d, 17-e, 17-f) were prepared, and the results of measurement according to the evaluation test method shown in Example 1 are shown in Table 2.

Example 18 To 100 parts of the resin obtained in Synthesis Example 18, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-18) was produced.

Next, a mixture of 200 parts of the base material (A-18) and 23 parts of the curing agent (B-2) used in Example 1 was used, and the specimen (18-a , 1
8-b, 18-c, 18-d, 18-e, 18-f) were prepared, and the results of measurement according to the evaluation test method shown in Example 1 are shown in Table 2.

Example 19 To 100 parts of the resin obtained in Synthesis Example 19, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator were used. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-19) was prepared.

Then, a mixture of 200 parts of the base material (A-19) and 16 parts of the curing agent (B-2) used in Example 1 was used. , 1
9-b, 19-c, 19-d, 19-e and 19-f) were prepared, and the results of measurement according to the evaluation test method shown in Example 1 are shown in Table 2.

Example 20 To 100 parts of the resin obtained in Synthesis Example 20, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-20) was produced.

Then, a mixture of 200 parts of the base material (A-20) and 54 parts of the curing agent (B-2) used in Example 1 was used. , 2
0-b, 20-c, 20-d, 20-e, and 20-f) were prepared, and the results of measurement according to the evaluation test method shown in Example 1 are shown in Table 2.

Comparative Example 1 To 100 parts of the resin obtained in Synthesis Example 21, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-21) was produced.

Next, a mixture of 200 parts of the base material (A-21) and 10 parts of the curing agent (B-2) used in Example 1 was used in the same manner as in Example 1 to obtain a sample (21-a). , 2
1-b, 21-c, 21-d, 21-e, 21-f) were prepared, and the results of measurement according to the evaluation test method shown in Example 1 are shown in Table 2.

Comparative Example 2 Based on 100 parts of the resin obtained in Synthesis Example 23, 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base material. (A-22) was produced.

Then, a mixture of 200 parts of the base material (A-22) and 62 parts of the curing agent (B-2) used in Example 2 was used, and the specimen (22-a , 2
2-b, 22-c, 22-d, 22-e and 22-f) were prepared, and the results of measurement according to the evaluation test method shown in Example 1 are shown in Table 2.

Comparative Example 3 20 parts of butyl cellosolve as a solvent, 10 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, and 2,2-dimethoxy- as a photopolymerization initiator were added to 100 parts of the resin obtained in Synthesis Example 24. 5 parts of 2-phenylacetophenone, 57 parts of a filler barium sulfate, 2 parts of a curing agent dicyandiamide, 5 parts of finely divided silica, and 1 part of a coloring pigment (phthalocyanine green) are added, and the mixture is sufficiently kneaded with a three-roll mill to prepare a photosensitive resin composition base. (A-23) was produced.

Next, using a mixture of 200 parts of the base material (A-23) and 27 parts of the curing agent (B-1) used in Example 1, the specimen (23-a , 2
3-b, 23-c, 23-d, 23-e, and 23-f) were prepared, and the results of measurement according to the evaluation test method shown in Example 1 are shown in Table 2.

[0117]

[Table 1]

[0118]

[Table 2]

[0119]

According to the present invention, crack resistance, adhesion to copper, dryness to the touch, heat resistance, resolution, flexibility, developability, water resistance, electrical characteristics, and other requirements Provided is a photosensitive resin composition that has excellent characteristics, can be highly productive and can be manufactured at low cost, has low solvent evaporation in the working environment, and is particularly suitable for use in alkali-developed build-up type multilayer printed circuit boards. Is done.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA00 AA02 AA04 AA10 AA13 AA14 AA20 AB15 AC01 AC08 AD01 BC12 BC14 BC31 BC34 BC43 BC51 BC55 BC65 BC72 BC73 BC82 BC85 BC86 CA00 CC03 CC17 FA17 5E314 AA27 AA31 AA32 CC02 FFFF19 GG08 GG11 GG24 5E346 CC09 CC52 DD03 EE31 HH01 HH18 HH31

Claims (8)

[Claims] 1. A method comprising reacting (A) a novolak epoxy compound and / or a glycol epoxy compound, an unsaturated monobasic acid and a saturated monobasic acid, and further reacting a saturated or unsaturated polybasic anhydride. Photosensitive resin,
A photosensitive resin composition comprising (B) an epoxy resin, (C) a photopolymerization initiator, and (D) a polymerizable unsaturated compound and / or a solvent. 2. The photosensitive resin composition according to claim 1, wherein the photosensitive resin (A) contains 70 to 100% of a novolak epoxy compound and 0 to 30% of a glycol epoxy compound. 3. The photosensitive resin (A), wherein the novolak epoxy compound comprises a phenol novolak epoxy compound, a cresol novolak epoxy compound, a dicyclopentadiene-phenol polyaddition epoxy compound, or a combination thereof. 3. The photosensitive resin composition according to item 1. 4. In the photosensitive resin (A), an unsaturated monobasic acid and a saturated monobasic acid are added in a total amount of 0.8 equivalent to 1.0 equivalent of an epoxy group of a novolak epoxy compound and / or a glycol epoxy compound. The reaction according to claim 1 or 2, wherein the reaction is carried out at a ratio of 0.2 to 0.9 equivalents of the unsaturated monobasic acid and 0.1 to 0.8 equivalents of the saturated monobasic acid. Photosensitive resin composition. 5. A photosensitive resin (A) having a novolak-type epoxy compound and / or a glycol-based epoxy compound, an unsaturated monobasic acid and a saturated monobasic acid, reacted with 1.0 mol of a hydroxyl group of a reaction product. 5. The photosensitive resin composition according to claim 1, wherein the saturated or unsaturated polybasic acid anhydride is reacted in a ratio of 0.2 to 0.9 mol. 6. The photosensitive resin composition according to claim 1, wherein the epoxy resin (B) is mixed in an amount of 3 to 100 parts by weight based on 100 parts by weight of the photosensitive resin (A). 7. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator (C) is compounded in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the photosensitive resin (A). 8. The polymerizable unsaturated compound and / or the solvent (D) may be added in an amount of 1 to 100 parts by weight of the photosensitive resin (A).
The photosensitive resin composition according to claim 1, which is added in an amount of 0 to 200 parts by weight.