JP2003021898A - Photosensitive resin composition and its cured body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in photosensitivity and giving a cured body excellent in storage stability, resolution, surface gloss, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance, PCT resistance, thermal shock resistance, etc. SOLUTION: In the photosensitive resin composition containing a resin (A) soluble in an aqueous alkali solution, a photopolymerization initiator (B), a photocrosslinker (C), a heat curable component (D) and a curing catalyst (E), the curing catalyst (E) is a compound having a 1,4-dihydropyridine backbone which may have an N-substituent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive resin composition and a cured product thereof, and more specifically, it is useful as a solder resist for a printed wiring board, a plating resist, an interlayer electrical insulating material for a multilayer printed wiring board, and a storage material. Stability,
Developability, electrical insulation, adhesion, solder heat resistance, chemical resistance,
The present invention relates to a resin composition that gives a cured product having excellent gold plating resistance and the like, and a cured product thereof.

[0002]

2. Description of the Related Art Conventionally, a method of forming a solder resist by screen printing using a thermosetting ink or a photocurable ink has been widely used. However, when this method is used, the accuracy of the obtained resist pattern decreases due to phenomena such as bleeding, bleeding, and sagging during printing, and it is possible to cope with recent miniaturization, high density, and high functionality of printed circuit boards. It's gone. With the increase in the density of such circuit wiring, a photo solder resist for forming a pattern by a photographic method has been widely used. Of these, materials that can be developed with an aqueous alkaline solution have become mainstream, and for example, JP-A-61-2438.
69, JP-A-64-62375, JP-A-3.
No. 253093 and Japanese Patent Publication No. 1-54390 disclose that a phenolic or o-cresol novolac type epoxy resin is reacted with an unsaturated monobasic acid, and a saturated or unsaturated polybasic acid anhydride is further reacted. A resist composition using the obtained resin is disclosed. JP-A-3-289
No. 656, a composition using a resin obtained by copolymerizing glycidyl (meth) acrylate or the like as a constituent component and modifying an epoxy group in the same manner as the above-mentioned resin is also disclosed in JP-A No. 2-9.
No. 7513 discloses ethylene obtained by reacting a reaction product of an epoxy compound of a condensation product of a phenol and an aromatic aldehyde having a phenolic hydroxyl group with (meth) acrylic acid with a polybasic carboxylic acid or an anhydride thereof. A composition using a polycarboxylic acid resin containing a polymerizable unsaturated group is disclosed. However, since these compositions contain a curing catalyst for reacting a photosensitive resin and a curing agent, they have low stability and are mainly two-component compositions in which the photosensitive resin and the curing agent are separated. There is.

On the other hand, in recent years, a dry film type solder resist has been desired in consideration of work environment and global environment. This has a structure in which the resin composition is sandwiched between a support film and a protective film, but since it contains a photosensitive resin, a curing agent, and a curing catalyst at the same time, the storage stability is extremely low, and the storage stability is below 0 ° C. It must be refrigerated or frozen, which makes handling complicated.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a one-component type or a dry film instead of a two-component type in which a photosensitive resin and a curing agent are separated, and to provide storage stability, developability, It is an object of the present invention to provide a resin composition which gives a cured product excellent in electrical insulation, adhesion, solder heat resistance, chemical resistance, gold plating resistance and the like.

[0005]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have developed an aqueous alkali solution resin (A), a photopolymerization initiator (B), a photocrosslinking agent (C), and a thermosetting component (D). )
As a result of earnest research on the photosensitive resin composition containing the curing catalyst (E), the present invention has been completed. That is,
The present invention includes (1) an aqueous alkaline solution-soluble resin (A), a photopolymerization initiator (B), a photocrosslinking agent (C), and a thermosetting component (D).
In the photosensitive resin composition containing the curing catalyst (E), the curing catalyst (E) may have an N-substituent,
4- (2′-nitro, wherein the photosensitive resin composition is a compound having a 1,4-dihydropyridine skeleton, and (2) the curing catalyst (E) may have an N-substituent. The photosensitive resin composition according to (1), which is a compound having a phenyl) -1,4-dihydropyridine skeleton,
(3) The photosensitive resin composition according to any one of (1) and (2), wherein the curing catalyst (E) is a compound represented by the following formula (1):

[0006]

[Chemical 2] (In the formula, R ₁ , R ₂ , R ₃ , and R ₄ represent a hydrogen atom, a halogen atom, a nitro group, or an alkyl group having 1 to 3 carbon atoms, and R ₅ , R ₆ are a nitrile group, -COOR. _{1 0} or indicates _{-COR 11,, R 7, R} 8 represents a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms, _{R 9} is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or aryl, Represents a group, and R ₁₀ and R ₁₁ represent a hydrogen atom or a carbon number of 1 to 3.
Is an alkyl group. )

(4) Alkaline aqueous solution soluble resin (A)
Is a compound having a carboxyl group in the molecule, wherein the photosensitive resin composition according to any one of (1) to (3) and (5) the aqueous alkaline solution-soluble resin (A) are 2 in the molecule. An epoxycarboxylate compound obtained by reacting the above epoxy compound (a) having an epoxy group with a monocarboxylic acid compound (c) having an unsaturated double bond in the molecule, and a polybasic acid anhydride (d) The photosensitive resin composition according to any one of (1) to (4), which is a reaction product of (6), wherein (6) the epoxy equivalent of the epoxy compound (a) having two or more epoxy groups in the molecule is , 90
The photosensitive resin composition according to any one of (1) to (5), which is an epoxy compound in the range of to 600 g / equivalent, (7) a monocarboxylic acid compound having an unsaturated double bond in the molecule. (C) is a monocarboxylic acid selected from (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or one or more selected from cinnamic acid groups ( 1) The photosensitive resin composition according to any one of 6), (8) the polybasic acid anhydride (d) is succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride. , Itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4
-Methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride selected from the group consisting of one or more selected from (1) to (7). The resin composition and (9) the alkali aqueous solution-soluble resin (A) have a solid acid value of 30 to 150 mg.
The photosensitive resin composition according to any one of (1) to (8) in the range of KOH / g, (10) the photosensitive resin composition according to any one of (1) to (9). A film coated with the product, (11) a cured product of the photosensitive resin composition according to any one of (1) to (10), (12)
A substrate having a layer of the cured product according to (11), (13)
An object is to provide an article having the substrate according to (12).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive resin composition of the present invention comprises an alkali aqueous solution-soluble resin (A), a photopolymerization initiator (B),
Photocrosslinking agent (C), thermosetting component (D) and curing catalyst (E)
In the photosensitive resin composition containing, the curing catalyst (E) is a compound having a 1,4-dihydropyridine skeleton, which may have an N-substituent.

The greatest feature of the curing catalyst (E) used in the photosensitive resin composition of the present invention is that it is structurally converted into a basic substance having a strong catalytic activity by being irradiated with ultraviolet rays. The former is that since it has no catalytic activity, it has excellent storage stability even if it contains a photosensitive resin, a curing agent, and a curing catalyst at the same time. An example of a radiation-curable resin composition for forming a cured product of a silicon-containing polymer using 1,4-dihydropyridines as such a curing catalyst (E) is disclosed in JP-A-8-21116 and JP-A-8-216116. 9-268228, JP-A-10-83080.
The proposal is made in the publication.

The curing catalyst (E) used in the photocurable resin composition of the present invention may have an N-substituent.
Any compound having a 1,4-dihydropyridine skeleton can be used, but an N-substituted compound that easily undergoes an intramolecular redox reaction by a nitro group activated by ultraviolet irradiation to convert the structure into a basic substance A compound having a 4- (2′-nitrophenyl) -1,4-dihydropyridine skeleton, which may have a group, is preferable, and particularly it has high photoreactivity, good compatibility, and structurally converted basicity. A compound represented by the above formula (1) having a high catalytic activity of the substance is preferable. These compounds have a maximum absorption in the range of 300 to 400 nm and are used for curing a photocurable resin. Specifically, they are generally used in the industrial field such as adhesives, paints and electronic materials. It is in good agreement with the irradiation wavelength of the UV irradiator. Furthermore, these compounds are thermally stable and do not easily cause structural conversion into basic substances, and the maximum absorption between 300 and 400 nm is due to structural conversion into basic substances by light irradiation. It has the characteristic of fading, and even in a relatively thick film, it can reduce the internal filter effect and allow light to fully penetrate to the inside and the lower part of the film, while at the same time functioning as an internal contrast enhancement layer and transferring. It works to increase the resolution of the pattern.

Specific examples of such compounds include 4- (2'-nitrophenyl) -2,6-dimethyl-
3,5-diacetoxy-1,4-dihydropyridine 4- (2'-nitrophenyl) -2,6-diethyl-
3,5-diacetoxy-1,4-dihydropyridine 4- (2'-nitrophenyl) -2,6-dimethyl-
3,5-Dicyano-1,4-dihydropyridine 4- (2'-nitrophenyl) -2,6-diethyl-
3,5-Dicyano-1,4-dihydropyridine 4- (2'-nitrophenyl) -2,6-dimethyl-
3,5-dimethoxycarbonyl-1,4-dihydropyridine 4- (2'-nitrophenyl) -2,6-diethyl-
3,5-dimethoxycarbonyl-1,4-dihydropyridine 4- (2′-nitrophenyl) -2,6-dimethyl-
3,5-diethoxycarbonyl-1,4-dihydropyridine 4- (2'-nitrophenyl) -2,6-diethyl-
3,5-diethoxycarbonyl-1,4-dihydropyridine 4- (2'-nitrophenyl) -2,6-dimethyl-
3,5-dipropoxycarbonyl-1,4-dihydropyridine 4- (2'-nitrophenyl) -2,6-diethyl-
3,5-dipropoxycarbonyl-1,4-dihydropyridine 4- (2'-nitrophenyl) -2,6-dimethyl-
3,5-Dibutoxycarbonyl-1,4-dihydropyridine 4- (2'-nitrophenyl) -2,6-diethyl-
3,5-Dibutoxycarbonyl-1,4-dihydropyridine 4- (5'-chloro-2'-nitrophenyl) -2,6
-Dimethyl-3,5-diacetoxy-1,4-dihydropyridine 4- (5'-chloro-2'-nitrophenyl) -2,6
-Diethyl-3,5-diacetoxy-1,4-dihydropyridine 4- (5'-chloro-2'-nitrophenyl) -2,6
-Dimethyl-3,5-dicyano-1,4-dihydropyridine 4- (5'-chloro-2'-nitrophenyl) -2,6
-Diethyl-3,5-dicyano-1,4-dihydropyridine 4- (5'-chloro-2'-nitrophenyl) -2,6
-Dimethyl-3,5-dimethoxycarbonyl-1,4-
Dihydropyridine 4- (5'-chloro-2'-nitrophenyl) -2,6
-Diethyl-3,5-dimethoxycarbonyl-1,4-
Dihydropyridine 4- (5'-chloro-2'-nitrophenyl) -2,6
-Dimethyl-3,5-diethoxycarbonyl-1,4-
Dihydropyridine 4- (5'-chloro-2'-nitrophenyl) -2,6
-Diethyl-3,5-diethoxycarbonyl-1,4-
Dihydropyridine 4- (5'-chloro-2'-nitrophenyl) -2,6
-Dimethyl-3,5-dipropoxycarbonyl-1,4
-Dihydropyridine 4- (5'-chloro-2'-nitrophenyl) -2,6
-Diethyl-3,5-dipropoxycarbonyl-1,4
-Dihydropyridine 4- (5'-chloro-2'-nitrophenyl) -2,6
-Dimethyl-3,5-dibutoxycarbonyl-1,4-
Dihydropyridine 4- (5'-chloro-2'-nitrophenyl) -2,6
-Diethyl-3,5-dibutoxycarbonyl-1,4-
Dihydropyridine 4- (2 ', 4'-dinitrophenyl) -2,6-dimethyl-3,5-diacetoxy-1,4-dihydropyridine 4- (2', 4'-dinitrophenyl) -2,6-diethyl- 3,5-diacetoxy-1,4-dihydropyridine 4- (2 ', 4'-dinitrophenyl) -2,6-dimethyl-3,5-dicyano-1,4-dihydropyridine 4- (2', 4'- Dinitrophenyl) -2,6-diethyl-3,5-dicyano-1,4-dihydropyridine 4- (2 ', 4'-dinitrophenyl) -2,6-dimethyl-3,5-dimethoxycarbonyl-1,4 -Dihydropyridine 4- (2 ', 4'-dinitrophenyl) -2,6-diethyl-3,5-dimethoxycarbonyl-1,4-dihydropyridine 4- (2', 4'-dinitrophenyl) -2,6- The Tyl-3,5-diethoxycarbonyl-1,4-dihydropyridine 4- (2 ′, 4′-dinitrophenyl) -2,6-diethyl-3,5-diethoxycarbonyl-1,4-dihydropyridine 4- ( 2 ', 4'-dinitrophenyl) -2,6-dimethyl-3,5-dipropoxycarbonyl-1,4-dihydropyridine 4- (2', 4'-dinitrophenyl) -2,6-diethyl-3, 5-dipropoxycarbonyl-1,4-dihydropyridine 4- (2 ', 4'-dinitrophenyl) -2,6-dimethyl-3,5-dibutoxycarbonyl-1,4-dihydropyridine 4- (2', 4 '-Dinitrophenyl) -2,6-diethyl-3,5-dibutoxycarbonyl-1,4-dihydropyridine 4- (5'-methyl-2'-nitrophenyl) -2,6
-Dimethyl-3,5-diacetoxy-1,4-dihydropyridine 4- (5'-methyl-2'-nitrophenyl) -2,6
-Diethyl-3,5-diacetoxy-1,4-dihydropyridine 4- (5'-methyl-2'-nitrophenyl) -2,6
-Dimethyl-3,5-dicyano-1,4-dihydropyridine 4- (5'-methyl-2'-nitrophenyl) -2,6
-Diethyl-3,5-dicyano-1,4-dihydropyridine 4- (5'-methyl-2'-nitrophenyl) -2,6
-Dimethyl-3,5-dimethoxycarbonyl-1,4-
Dihydropyridine 4- (5'-methyl-2'-nitrophenyl) -2,6
-Diethyl-3,5-dimethoxycarbonyl-1,4-
Dihydropyridine 4- (5'-methyl-2'-nitrophenyl) -2,6
-Dimethyl-3,5-diethoxycarbonyl-1,4-
Dihydropyridine 4- (5'-methyl-2'-nitrophenyl) -2,6
-Diethyl-3,5-diethoxycarbonyl-1,4-
Dihydropyridine 4- (5'-methyl-2'-nitrophenyl) -2,6
-Dimethyl-3,5-dipropoxycarbonyl-1,4
-Dihydropyridine 4- (5'-methyl-2'-nitrophenyl) -2,6
-Diethyl-3,5-dipropoxycarbonyl-1,4
-Dihydropyridine 4- (5'-methyl-2'-nitrophenyl) -2,6
-Dimethyl-3,5-dibutoxycarbonyl-1,4-
Dihydropyridine 4- (5'-methyl-2'-nitrophenyl) -2,6
-Diethyl-3,5-dibutoxycarbonyl-1,4-
Dihydropyridine N-methyl-4- (2'-nitrophenyl) -2,6-
Dimethyl-3,5-diacetoxy-1,4-dihydropyridine N-methyl-4- (2'-nitrophenyl) -2,6-
Diethyl-3,5-diacetoxy-1,4-dihydropyridine N-methyl-4- (2′-nitrophenyl) -2,6-
Dimethyl-3,5-dicyano-1,4-dihydropyridine N-methyl-4- (2'-nitrophenyl) -2,6-
Diethyl-3,5-dicyano-1,4-dihydropyridine N-methyl-4- (2'-nitrophenyl) -2,6-
Dimethyl-3,5-dimethoxycarbonyl-1,4-dihydropyridine N-methyl-4- (2'-nitrophenyl) -2,6-
Diethyl-3,5-dimethoxycarbonyl-1,4-dihydropyridine N-methyl-4- (2′-nitrophenyl) -2,6-
Dimethyl-3,5-diethoxycarbonyl-1,4-dihydropyridine N-methyl-4- (2'-nitrophenyl) -2,6-
Diethyl-3,5-diethoxycarbonyl-1,4-dihydropyridine N-methyl-4- (2'-nitrophenyl) -2,6-
Dimethyl-3,5-dipropoxycarbonyl-1,4-
Dihydropyridine N-methyl-4- (2'-nitrophenyl) -2,6-
Diethyl-3,5-dipropoxycarbonyl-1,4-
Dihydropyridine N-methyl-4- (2'-nitrophenyl) -2,6-
Dimethyl-3,5-dibutoxycarbonyl-1,4-dihydropyridine N-methyl-4- (2'-nitrophenyl) -2,6-
Diethyl-3,5-dibutoxycarbonyl-1,4-dihydropyridine N-ethyl-4- (2′-nitrophenyl) -2,6-
Dimethyl-3,5-diacetoxy-1,4-dihydropyridine N-ethyl-4- (2'-nitrophenyl) -2,6-
Diethyl-3,5-diacetoxy-1,4-dihydropyridine N-ethyl-4- (2′-nitrophenyl) -2,6-
Dimethyl-3,5-dicyano-1,4-dihydropyridine N-ethyl-4- (2'-nitrophenyl) -2,6-
Diethyl-3,5-dicyano-1,4-dihydropyridine N-ethyl-4- (2'-nitrophenyl) -2,6-
Dimethyl-3,5-dimethoxycarbonyl-1,4-dihydropyridine N-ethyl-4- (2'-nitrophenyl) -2,6-
Diethyl-3,5-dimethoxycarbonyl-1,4-dihydropyridine N-ethyl-4- (2'-nitrophenyl) -2,6-
Dimethyl-3,5-diethoxycarbonyl-1,4-dihydropyridine N-ethyl-4- (2'-nitrophenyl) -2,6-
Diethyl-3,5-diethoxycarbonyl-1,4-dihydropyridine N-ethyl-4- (2'-nitrophenyl) -2,6-
Dimethyl-3,5-dipropoxycarbonyl-1,4-
Dihydropyridine N-ethyl-4- (2'-nitrophenyl) -2,6-
Diethyl-3,5-dipropoxycarbonyl-1,4-
Dihydropyridine N-ethyl-4- (2'-nitrophenyl) -2,6-
Dimethyl-3,5-dibutoxycarbonyl-1,4-dihydropyridine N-ethyl-4- (2'-nitrophenyl) -2,6-
Diethyl-3,5-dibutoxycarbonyl-1,4-dihydropyridine N-phenyl-4- (2′-nitrophenyl) -2,6
-Dimethyl-3,5-diacetoxy-1,4-dihydropyridine N-phenyl-4- (2'-nitrophenyl) -2,6
-Diethyl-3,5-diacetoxy-1,4-dihydropyridine N-phenyl-4- (2'-nitrophenyl) -2,6
-Dimethyl-3,5-dicyano-1,4-dihydropyridine N-phenyl-4- (2'-nitrophenyl) -2,6
-Diethyl-3,5-dicyano-1,4-dihydropyridine N-phenyl-4- (2'-nitrophenyl) -2,6
-Dimethyl-3,5-dimethoxycarbonyl-1,4-
Dihydropyridine N-phenyl-4- (2'-nitrophenyl) -2,6
-Diethyl-3,5-dimethoxycarbonyl-1,4-
Dihydropyridine N-phenyl-4- (2'-nitrophenyl) -2,6
-Dimethyl-3,5-diethoxycarbonyl-1,4-
Dihydropyridine N-phenyl-4- (2'-nitrophenyl) -2,6
-Diethyl-3,5-diethoxycarbonyl-1,4-
Dihydropyridine N-phenyl-4- (2'-nitrophenyl) -2,6
-Dimethyl-3,5-dipropoxycarbonyl-1,4
-Dihydropyridine N-phenyl-4- (2'-nitrophenyl) -2,6
-Diethyl-3,5-dipropoxycarbonyl-1,4
-Dihydropyridine N-phenyl-4- (2'-nitrophenyl) -2,6
-Dimethyl-3,5-dibutoxycarbonyl-1,4-
Dihydropyridine N-phenyl-4- (2'-nitrophenyl) -2,6
-Diethyl-3,5-dibutoxycarbonyl-1,4-
Dihydropyridine etc. are mentioned. These compounds are
For example, it can be synthesized by the method described in West German Laid-Open Publication No. 2003148 or West German Laid-Open Publication No. 2005116.

The proportion of these curing catalysts (E) used is usually 0.1 to 4 when the solid content of the composition is 100 parts by weight.
0 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 1 to 25 parts by weight. If this amount is less than 0.1 part by weight, the amount of the basic substance produced after light irradiation may be small and the curing rate may be significantly reduced.
If it exceeds the weight part, the internal filter effect is strong even if light irradiation is performed, and the intramolecular redox reaction inside or under the film may not be completed, which may cause defective internal curing or coloring. It is recommended to add 0.1 part by weight or more to 4
It is preferable that the amount is 0 parts by weight or less.

The alkali aqueous solution-soluble resin (A) used for obtaining the photosensitive resin composition of the present invention may be any as long as it is soluble in an aqueous solution having a pH of 7 or more. In order to enhance the solubility, it is particularly preferable to have a carboxyl group in the molecule. Specific examples of the compound satisfying this condition include, for example,
(A) A polybasic acid anhydride, a compound having an ethylenically unsaturated double bond in the molecule and a hydroxyl group in the molecule, and a compound having a hydroxyl group in the molecule, if necessary, are added to carry out a polycondensation reaction. The resulting compound, (i) a compound having an ethylenically unsaturated double bond in the molecule, and a compound obtained by addition reaction of a polybasic acid anhydride to a resin having a hydroxyl group in the molecule,
(U) A compound obtained by urethanizing a compound having an ethylenically unsaturated double bond in the molecule and having a hydroxyl group in the molecule and a carboxylic acid compound having a hydroxyl group in the molecule with an isocyanate compound, (e) (meta) ) Styrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) copolymerizable with acrylic acid
Acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, vinyl acetate, copolymers with monomers such as ethylene and propylene, (o) styrene-maleic anhydride copolymer and half-esters with alcohols Compound (or) an epoxycarboxylate compound obtained by reacting an epoxy compound (a) having two or more epoxy groups in the molecule with a monocarboxylic acid compound (c) having an unsaturated double bond in the molecule Examples thereof include alkaline aqueous solution-soluble epoxycarboxylate compounds, which are reaction products of polybasic acid anhydride (d) with the balance of developability, adhesion, solder heat resistance, chemical resistance, gold plating resistance, etc. Epoxy carboxylate compounds soluble in alkaline aqueous solution are particularly preferable.

Specific examples of the epoxy compound (a) having two or more epoxy groups in the molecule include, for example, phenyldiglycidyl ether such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, bisphenol- A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, 2,2-bis (4-
Hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compound or other bisphenol type epoxy compound, hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin,
Hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,
2-bis (4-hydroxyphenyl) -1,1,1,
Hydrogenated bisphenol type epoxy compounds such as epoxy compounds of 3,3,3-hexafluoropropane, brominated bisphenol-A type epoxy resins, halogenated bisphenol type epoxy compounds such as brominated bisphenol-F type epoxy resins, cyclohexanedimethanol Alicyclic diglycidyl ether compounds such as diglycidyl ether compounds, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, aliphatic diglycidyl ether compounds such as diethylene glycol diglycidyl ether, polysulfide diglycidyl Polysulfide type epoxy resin such as ether, biphenol type epoxy compound, biphenol type epoxy resin such as bixylenol type epoxy compound, phenol novolac type epoxy resin Resins, cresol novolac type epoxy resins, novolac type epoxy resins such as xylenol novolac type epoxy resins, polyfunctional epoxy resins such as trisphenolmethane type epoxy resins, heterocyclic skeleton epoxy resins such as triglycidyl isocyanurate, and the like. The epoxy equivalent of is 90 to 600
Compounds in the g / equivalent range are particularly preferred.

Commercially available products of these epoxy compounds include:
For example, Epicoat 828, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 100
4 (all manufactured by Japan Epoxy Resin), Epomic R-140, Epomic R-301, Epomic R-3
04 (all manufactured by Mitsui Chemicals), DER-331, DER
-332, DER-324 (all manufactured by Dow Chemical Co.), Epicron 840, Epiclon 850 (all manufactured by Dainippon Ink) UVR-6410 (manufactured by Union Carbide Co.), YD-8125 (manufactured by Toto Kasei Co., Ltd.), etc. Bisphenol-A type epoxy resin, UVR-6490 (manufactured by Union Carbide Co.), YDF-2001, YDF-2
004, YDF-8170 (all manufactured by Tohto Kasei Co., Ltd.),
Bisphenol-F type epoxy resins such as Epicron 830 and Epicron 835 (all manufactured by Dainippon Ink and Chemicals), H
BPA-DGE (Maruzen Petrochemical Co., Ltd.), Lycaredin HBE
− Hydrogenated bisphenols such as 100 (manufactured by Shin Nippon Rika) −
A type epoxy resin, DER-513, DER-514,
Brominated bisphenol-A type epoxy resin such as DER-542 (all manufactured by Dow Chemical Co., Ltd.), Celoxide 2021 (manufactured by Daicel), Rikaresin DME-100
(Nippon Rika), EX-216 (Nagase Kasei) and other alicyclic epoxy resins, ED-503 (Asahi Denka), Licarezin W-100 (Nippon Rika), EX-212, E
X-214, EX-850 (both manufactured by Nagase Kasei), etc., aliphatic diglycidyl ether compound, FLEP-5
0, FLEP-60 (all manufactured by Toraythiocol), etc., polysulfide type diglycidyl ether compound, NC
-3000P, NC-3000S (Nippon Kayaku), YX
Biphenol-type epoxy compounds such as -4000 (manufactured by Japan Epoxy Resin).

Examples of the phenol novolac type epoxy resin include Epicron N-770 (manufactured by Dainippon Ink and Chemicals, Inc.), D.I. E. Examples include N438 (manufactured by Dow Chemical Co., Ltd.), Epicoat 154 (manufactured by Yuka Shell Epoxy Co., Ltd.), RE-306 (manufactured by Nippon Kayaku Co., Ltd.) and the like. Examples of the cresol novolac type epoxy resin include Epicron N-695 (manufactured by Dainippon Ink and Chemicals, Inc.), EOCN-102S, EOCN-103.
S, EOCN-104S (Nippon Kayaku Co., Ltd.), UVR
-6650 (made by Union Carbide), ESCN-1
95 (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

Examples of the trishydroxyphenylmethane type epoxy resin include EPPN-503 and EPPN-
502H, EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.),
TACTIX-742 (manufactured by Dow Chemical Co.), Epicoat E1032H60 (manufactured by Yuka Shell Epoxy Co., Ltd.)
Etc. Examples of the dicyclopentadiene phenol type epoxy resin include Epiclon EXA-720.
0 (manufactured by Dainippon Ink and Chemicals, Inc.), TACTIX-
556 (manufactured by Dow Chemical Co.) and the like.

Examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000P, NC-3000S (Nippon Kayaku Co., Ltd.), YX-4.
000 (produced by Yuka Shell Epoxy Co., Ltd.) and bixylenol type epoxy resin, YL-6121 (produced by Yuka Shell Epoxy Co., Ltd.) and the like. Examples of the bisphenol A novolac type epoxy resin include Epiclon N-8.
80 (manufactured by Dainippon Ink and Chemicals, Inc.), Epicoat E
157S75 (produced by Yuka Shell Epoxy Co., Ltd.) and the like.

Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.) and EXA-
4750 (manufactured by Dainippon Ink and Chemicals, Inc.) and the like. Examples of the alicyclic epoxy resin include EHPE-
3150 (manufactured by Daicel Chemical Industries, Ltd.) and the like. Examples of the heterocyclic epoxy resin include TEPl
C, TEPIC-L, TEPIC-H, TEPIC-S
(Both manufactured by Nissan Chemical Industries, Ltd.) and the like.

Examples of the monocarboxylic acid compound (c) having an unsaturated double bond in the molecule used for obtaining the photosensitive resin composition of the present invention include acrylic acids, crotonic acid and α-cyanocinnamic acid. , Cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid with an unsaturated group-containing monoglycidyl compound. Examples of acrylic acids include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, saturated or unsaturated dibasic acid anhydrides, and (meth) acrylate derivatives having one hydroxyl group in one molecule. And a half-ester which is an equimolar reaction product, and a half-ester which is an equimolar reaction product of a saturated or unsaturated dibasic acid and a monoglycidyl (meth) acrylate derivative. From the standpoint of sensitivity, it is particularly preferable to use (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid.

As the polybasic acid anhydride (d) used to obtain the photosensitive resin composition of the present invention, for example, any polybasic acid anhydride (d) that can easily react with an alcoholic hydroxyl group can be used. , Especially succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride One or two or more polybasic acid anhydrides (d) selected from one or two or more kinds from the acid group are listed. The polybasic acid anhydride (d) comprises an epoxy compound (a) having two or more epoxy groups in the molecule and a monocarboxylic acid (c) having an unsaturated double bond in the molecule, as described later. By adding to the alcoholic hydroxyl group generated by the reaction, it is half-esterified to generate a carboxylic acid. The generated carboxylic acid is indispensable for imparting the developability of the aqueous alkaline solution, and the acid value of the solid content of the aqueous alkaline resin (A) is 30 to 150 mg · KOH / g.
It is particularly preferable that Solid content acid value is 3
When the amount is less than 0 mg · KOH / g, the developability of the resin composition described below in the alkaline aqueous solution is remarkably lowered, and in the worst case, development is not possible, which is not preferable. On the other hand, the solid acid value is 1
If it exceeds 50 mg · KOH / g, the developability of the alkaline aqueous solution may be too high, and the development adhesion may be lowered, or in the worst case, the pattern may not be obtained.

The alkaline aqueous solution-soluble resin (A) used in the photosensitive resin composition of the present invention can be obtained as follows. That is, in the first reaction, the epoxy compound (a) is esterified with the monocarboxylic acid (c) having one or more unsaturated double bonds in the molecule, and in the second reaction, the polybasic acid is used. The anhydride (d) is subjected to an addition reaction.

The first reaction is solvent-free or a solvent having no alcoholic hydroxyl group, specifically, for example, ketones such as acetone, ethylmethylketone, cyclohexanone, benzene, toluene, xylene, tetramethylbenzene, etc. Aromatic hydrocarbons, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether and other glycol ethers, ethyl acetate, butyl acetate, methyl cellosolve Acetate, ethyl cellosolve acetate, butyl cellosolve acetate,
Carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate, etc., cyclic esters such as γ-butyrolactone, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. Petroleum-based solvent, etc., and the cross-linking agent (C) described later.
Can be used as a solvent to react these in an organic solvent alone or in a mixture thereof.

During the reaction, it is preferable to use a catalyst for promoting the reaction, and the amount of the catalyst used is usually 0.1 to 10% by weight based on the reactant. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably usually 5 to 60 hours. Examples of the catalyst used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, and chromium. Acetylacetonate,
Zirconium octanoate, dimethyl sulfide, diallyl sulfide, diallyl disulfide, thiodiglycol, 1,2-bis (2-hydroxyethylthio) ethane, 1,4-bis (2-hydroxyethylthio) butane, diphenyl disulfide, dibenzyl Disulfide, dibutyl disulfide, 3,3'-dithiopropionic acid, 2,2'-dithiodiethanol, ethyl methylthiopropionate, thiodipropionic acid, dioctyl thiodipropionate, dimethyl thiodipropionate, 1,4
-Dithiane, 1,3-dithiane, thiophene, thiophenone, 1,4-thioxane, thionaphthene, thianthrene, γ-thiobutyrolactone, thiotetronic acid, thioxanthen-9-one, dimethyl sulfoxide, tetramethylene sulfone and the like. .

In the second reaction, after the completion of the first reaction, the polybasic acid anhydride (d) is charged and reacted in an amount calculated so that the acid value of the solid content after the reaction is in the above range. Obtained by The reaction temperature is preferably 60 to 150 ° C., and the reaction time is 1 to 10 hours.

Specific examples of the photopolymerization initiator (B) used in the photosensitive resin composition of the present invention include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; Acetophenone, 2,
2-dimethoxy-2-phenylacetophenone, 2,2
-Diethoxy-2-phenylacetophenone, 2,2-
Dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone,
2-Methyl-1- [4- (methylthio) phenyl] -2
-Acetophenones such as morpholinopropan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; 2,4-
Thioxanthones such as diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,
Benzophenones such as 4′-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. As the addition ratio of these, the solid content of the photosensitive resin composition is 100% by weight.
, 1 to 30% by weight, preferably 2 to 2
It is 5% by weight. These can be used alone or as a mixture of two or more kinds.

Further, a tertiary amine such as triethanolamine or methyldiethanolamine, and an accelerator such as a benzoic acid derivative such as N, N-dimethylaminobenzoic acid ethyl ester or N, N-dimethylaminobenzoic acid isoamyl ester are used. It can be used in combination. The amount of these accelerators added is preferably 100% by weight or less with respect to the photopolymerization initiator (B).

Specific examples of the photocrosslinking agent (C) used in the photosensitive resin composition of the present invention include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 1,4- Butanediol mono (meth) acrylate, carbitol (meth) acrylate, acryloylmorpholine, hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butane) Half ester which is the reaction product of acid anhydride (eg succinic acid-free, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) of polycarboxylic acid compound with diol mono (meth) acrylate etc. , Polyethylene glycol di (meth) acrylate Addition of ε-caprolactone to tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycene polypropoxytri (meth) acrylate, and neopene glycol hydroxypivalate. Di (meth) acrylate (for example, manufactured by Nippon Kayaku Co., Ltd., KAY
ARAD HX-220, HX-620, etc.), pentaerythritol tetra (meth) acrylate, poly (meth) acrylate of a reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly (meth) acrylate, mono- or polyglycidyl. Compounds (for example, butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
Hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether, etc. Epoxy (meth) which is a reaction product of (meth) acrylic acid An acrylate etc. can be mentioned. The addition ratio of these is usually 2 to 40% by weight, preferably 5 to 30% by weight, when the solid content of the photosensitive resin composition is 100% by weight.

Examples of the thermosetting component (D) used in the photosensitive resin composition of the present invention include epoxy compounds, oxetane compounds, oxazine compounds and the like. The thermosetting component (D) is particularly preferably used in order to obtain a cured coating film having a strong chemical resistance by reacting with a carboxyl group remaining in the resin coating film after photocuring by heating in the presence of a curing catalyst. .

As the epoxy compound used for the thermosetting component (D), the above-mentioned epoxy compounds exemplified as the epoxy compound (a) can be used as they are.

Specific examples of the oxetane compound used as the thermosetting component (D) include, for example, phenol, cresol, hydroquinone, resorcinol, pyrogallol, biphenol, bixylenol, bisphenol-.
A, bisphenol-F, bisphenol-S, polyvinylphenol, phenol novolac resins, cresol novolac resins, and other compounds obtained by oxetaneizing some or all of the phenolic hydroxyl groups, ethylene glycol, propylene glycol, polyethylene glycol,
Polypropylene glycol, pentaerythritol, trimethylolpropane, dipentaerythritol, tripentaerythritol, cyclohexyldimethanol,
Examples thereof include compounds in which part or all of alcoholic hydroxyl groups such as dicyclopentadienedimethanol are oxetaneized. These compounds are disclosed, for example, in JP-A-2000-3.
It can be synthesized by the method described in Japanese Patent No. 36133 or Japanese Patent Laid-Open No. 11-12261.

Specific examples of the oxazine compound used in the thermosetting component (D) include, for example, Bm type benzoxazine, Pa type benzoxazine, and Ba type benzoxazine (all manufactured by Shikoku Chemicals). Can be given. These compounds are disclosed, for example, in JP-A-2000-169456.
JP-A-11-209453, JP-A-11-209453
It can be synthesized by the method described in JP-A-80299 or JP-A-11-12258.

The addition ratio of the thermosetting component (D) is preferably 200% or less of the equivalent amount calculated from the acid value of the solid content of the aqueous alkali resin (A) and the amount used. If this amount exceeds 200%, the developability of the photosensitive resin composition of the present invention may be significantly reduced, which is not preferable.

Further, if necessary, various additives such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay, and other fillers, and thixotropy such as aerosil. Agents, phthalocyanine blue, phthalocyanine green, colorants such as titanium oxide, silicone, fluorine-based leveling agents and defoamers, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, and concentration adjusting agents such as solvents. It can be added for the purpose of enhancing the performance.

The photosensitive resin composition of the present invention can also be used as a dry film having a structure in which the resin composition is sandwiched between a support film and a protective film.

The photosensitive resin composition (liquid or film form) of the present invention is used as an insulating material between layers of electronic parts, a solder resist for optical waveguides or printed boards for connecting optical parts, a resist material for a coverlay, etc. Besides being useful, it can also be used as a color filter, a printing ink, a sealant, a paint, a coating agent, an adhesive, and the like.

The cured product of the present invention is obtained by curing the above-mentioned photosensitive resin composition of the present invention by irradiation with energy rays such as ultraviolet rays and heat treatment. Curing can be carried out by an ordinary method by irradiation with energy rays such as ultraviolet rays. For example, when irradiating with ultraviolet rays, an ultraviolet ray generator such as a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, an ultraviolet light emitting laser (excimer laser, etc.) may be used.

The cured product of the resin composition of the present invention is used, for example, as a resist film, an interlayer insulating material for a build-up construction method, and an optical waveguide for electric / electronic / optical parts such as a printed circuit board, an optoelectronic board and an optical board. It Specific examples of these include computers, home appliances, mobile devices, and the like. The thickness of this cured product layer is usually 0.5 to 160.
About μm, preferably about 1 to 100 μm.

The printed wiring board of the present invention can be obtained, for example, as follows. That is, when a liquid resin composition is used, it is applied to a printed wiring board with a film thickness of 0.5 to 160 μm by a method such as screen printing, spraying, roll coating, electrostatic coating or curtain coating. The photosensitive resin composition of the present invention is applied, and the coating film is usually 50-
A coating film can be formed by drying at a temperature of 110 ° C, preferably 60 to 100 ° C. Thereafter, the coating film is directly or indirectly irradiated with high energy rays such as ultraviolet rays at an intensity of about 10 to 2,000 mJ / cm ² through a photomask on which an exposure pattern such as a negative film is formed, and the unexposed portion is described below. Using a developing solution to
Develop by rocking immersion, brushing, scrubbing, etc. Then, if necessary, further irradiate with ultraviolet rays, and then usually 100 to 200 ° C., preferably 140 to 180.
By performing the heat treatment at a temperature of ° C, a printed wiring board having a permanent protective film having excellent gold plating properties and satisfying various properties such as heat resistance, solvent resistance, acid resistance, adhesion, and flexibility can be obtained.

Examples of the alkaline aqueous solution used for the development include inorganic alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate and potassium phosphate. Organic alkaline aqueous solutions such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine and the like can be used. Then, the pH of the alkaline aqueous solution is usually adjusted to 8 or more, preferably 8.5 to 14.

[0041]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. Examples 1, 2, 3, 4, and 5 were mixed at the compounding ratios shown in Table 1 and, if necessary, kneaded with a three-roll mill to obtain a photosensitive resin composition of the present invention. This was applied to a printed board by screen printing so that the dry film thickness was 15 to 25 μm, and the coating film was dried in a hot air dryer at 80 ° C. for 30 minutes. Then, ultraviolet rays were irradiated through a mask on which a circuit pattern was drawn, using an ultraviolet exposure device (Model HMW-680GW, manufactured by Oak Manufacturing Co., Ltd.). After that, spray development was performed with a 1% sodium carbonate aqueous solution to remove the resin in the portion not irradiated with ultraviolet rays. After washing with water and drying, the printed circuit board is dried with a hot air dryer at 150 ° C.
A heat-curing reaction was performed for 0 minutes to obtain a cured film. About the obtained cured product, as described below, storage stability, resolution, photosensitivity,
Surface gloss, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance, PCT resistance, and heat shock resistance were tested. The results are shown in Table 2. The test method and evaluation method are as follows.

(Storage stability) The dried film applied to the substrate was left at room temperature in the dark for 30 days. The developability was compared with that of the coating film even before standing. ○ ... ・ There is no difference in developability. Δ: Development residue remains slightly. × ・ ・ ・ ・ The film after standing cannot be developed at all.

(Resolution) A 50 μm negative pattern is brought into close contact with the dried coating film and exposed to ultraviolet rays having an integrated light amount of 200 mJ / cm ² . Next, it is developed with a 1% sodium carbonate aqueous solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the transfer pattern is observed with a microscope. The following criteria were used. ○: The pattern edge is a straight line and is resolved. × ... Peeling or jagged pattern edges.

(Photosensitivity) 21 steps of a step tablet (manufactured by Kodak Co., Ltd.) was brought into close contact with the dried coating film to obtain an integrated light amount of 50
It is exposed to ultraviolet light of 0 mJ / cm ² . Next, it is developed with a 1% sodium carbonate aqueous solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the number of steps of the coating film left undeveloped is confirmed.

(Surface gloss) 500 mJ on the dried coating film
Irradiate and expose with ultraviolet rays of / cm ² . Then, it is developed with a 1% sodium carbonate aqueous solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the cured film after drying is observed. The following criteria were used. ○ ・ ・ ・ ・ No cloudiness is observed × ・ ・ ・ ・ Slight cloudiness is observed

(Adhesiveness) According to JIS K5400,
Make 100 pieces of 1 mm sideways on the test piece and sell tape
^A peeling test was performed according to ^(R) . The peeling state of the first eye was observed and evaluated according to the following criteria. ○ ・ ・ ・ ・ No peeling × ・ ・ ・ ・ Peeling

(Pencil Hardness) The pencil hardness was evaluated according to JIS K5400.

(Solvent resistance) The test piece is immersed in isopropyl alcohol for 30 minutes at room temperature. After confirming that there is no abnormality in the appearance, a peeling test using Cellotape ^(R) was performed and evaluated according to the following criteria. ○ ・ ・ ・ ・ The appearance of the coating film is not abnormal and there is no blistering or peeling × ・ ・ ・ ・ The coating has blistering or peeling

(Acid resistance) The test piece is immersed in a 10% aqueous hydrochloric acid solution at room temperature for 30 minutes. After confirming that there is no abnormal appearance,
A peeling test using Cellotape ^(R) was performed and evaluated according to the following criteria. ○ ・ ・ ・ ・ The appearance of the coating film is not abnormal and there is no blistering or peeling × ・ ・ ・ ・ The coating has blistering or peeling

(Heat resistance) A rosin-based plaque was applied to the test piece and immersed in a solder bath at 260 ° C for 5 seconds. This was set as one cycle and repeated for three cycles. After allowing to cool to room temperature, a peeling test using Cellotape ^(R) was performed and evaluated according to the following criteria. 〇 ・ ・ The appearance of the coating film is not abnormal and there is no blistering or peeling × ・ ・ ・ ・ The coating has blistering or peeling

(Gold plating resistance) A test substrate was subjected to an acidic degreasing solution at 30 ° C. (made by Nippon McDermitt, Metex L-5).
(20 vol% aqueous solution of B) for 3 minutes, then washed with water, then immersed in 14.4 wt% ammonium persulfate aqueous solution for 3 minutes at room temperature, and then washed with water, and further test substrate was immersed in 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute. After dipping for a minute, it was washed with water.
Next, this substrate was immersed in a catalyst solution at 30 ° C (Meltex, 10 vol% aqueous solution of metal plate activator 350) for 7 minutes, washed with water, and a nickel plating solution at 85 ° C (Meltex Ni-Melplate Ni- 2 of 865M
It was dipped in a 0 vol% aqueous solution, pH 4.6) for 20 minutes to perform nickel plating, and then dipped in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute and washed with water. Then, the test board is
Immersing in a gold plating solution at ℃ (Meltex, an aqueous solution of 15% by volume of Aurolectroles UP and 3% by volume of potassium gold cyanide, pH 6) for 10 minutes to perform electroless gold plating, followed by rinsing with water and further heating with hot water at 60 ° C. It was soaked for a minute, washed with water and dried. A cellophane adhesive tape was attached to the obtained electroless gold-plated evaluation substrate, and the state of peeling was observed. ◯: No abnormality. X: Some peeling was observed.

(PCT resistance) After the test substrate was left in water at 121 ° C. and 2 atm for 96 hours, the appearance was checked for abnormality, and then a peeling test was performed using Cellotape ^(R) .
The following criteria evaluated. ○ ・ ・ ・ ・ The appearance of the coating film is not abnormal and there is no blistering or peeling × ・ ・ ・ ・ The coating has blistering or peeling

(Thermal shock resistance) The test piece was tested at -55 ° C / 30.
Min, 125 ° C./30 minutes as one cycle, a thermal history is added, and after 1000 cycles, the test piece is observed under a microscope.
The following criteria evaluated. ○ ・ ・ ・ ・ No cracks in the coating film × ・ ・ ・ ・ ・ ・ Cracks in the coating film

Table 1 Example 1 2 3 4 5 Injection resin solution A-1 1 35.17 A-2 2 35.17 A-3 3 35.17 A-4 4 48.57 A-5 5 48.57 Photopolymerization initiator (B) Irg.907 6 5.03 5.03 5.03 4.20 4.20 DETX-S 7 0.50 0.50 0.50 0.43 0.43 Photocrosslinking agent (C) DPHA 8 6.86 6.86 6.86 DPCA 9 3.17 HX-220 10 3.17 Thermosetting component (D) EOCN-1020 11 8.96 8.96 8.96 YX-4000 12 16.83 16.83 Curing catalyst (E) E-1 13 3.82 8.43 8.43 E-2 14 3.82 E-3 15 3.82 Filler BaSO ₄ 16 15.41 15.41 15.41 14.20 14.20 SiO ₂ 17 9.54 9.54 9.54 Pigment 18 0.58 0.58 0.58 0.43 0.43 Additive BYK -354 19 0.72 0.72 0.72 0.37 0.37 KS-66 20 0.72 0.72 0.72 0.37 0.37 Solvent CA 21 12.69 12.69 12.69 3.00 3.00

Note 1 Kayarad PCR-1072 (manufactured by Nippon Kayaku) Phenol novolac type epoxy acrylate tetrahydrophthalic anhydride adduct Solid content concentration 65% by weight Solid content Acid value: 100 mgK
OH / g 2 Kayarad CCR-1115 (manufactured by Nippon Kayaku) Cresol novolac type epoxy acrylate tetrahydrophthalic anhydride adduct Solid content concentration 65% by weight Solid content Acid value: 100 mgK
OH / g 3 Kayarad TCR-1286 (manufactured by Nippon Kayaku) Trisphenol methane type epoxy acrylate tetrahydrophthalic anhydride adduct solid content concentration 65% by weight Solid content acid value: 100 mg · K
OH / g 4 Kayarad ZAR-1035 (manufactured by Nippon Kayaku) Polyfunctional bisphenol-A type epoxy acrylate succinic anhydride adduct solid content concentration 65% by weight Solid content acid value: 100 mg · K
OH / g 5 Kayarad ZFR-1122 (manufactured by Nippon Kayaku) Polyfunctional bisphenol-F type epoxy acrylate tetrahydrophthalic anhydride adduct Solid content concentration 65 wt% Solid content Acid value: 100 mgK
OH / g 6 Irgacure 907 (manufactured by Bantico) 2-Methyl- (4- (methylthio) phenyl) -2-morpholino-1-propane 7 Kayacure DETX-S (Nippon Kayaku) 2,4-diethylthioxanthone 8 Kayarad DPHA (Nippon Kayaku) Dipentaerythritol hexa / pentaacrylate 9 Kayarad DPCA (Nippon Kayaku) Caprolactone modified dipentaerythritol hexaacrylate 10 Kayarad HX-220 (Nippon Kayaku) Caprolactone modified hydroxypivalate neopentyl glycol di Acrylate 11 EOCN-1020 (manufactured by Nippon Kayaku) Cresol novolac type epoxy resin Epoxy equivalent: 170 g / equivalent 12 YX-4000 (manufactured by Japan Epoxy Resin) Bifunctional bixylenol type epoxy resin 13 4- (2'-nitrophenyl) -2,6-dimethyl-3,5-dimethoxycarbonyl-1,4-dihydropyridine 14 4- (2'-nitrophenyl) -2,6-diethyl-3,5- Dimethoxycarbonyl-1,4-dihydropyridine 15 4- (2′-nitrophenyl) -2,6-diethyl-3,5-dicyano-1,4-dihydropyridine 16 Barium sulfate (made by Sakai Chemical) 17 Silica (made by Tatsumori) ) 18 Phthalocyanine green pigment 19 Leveling agent (manufactured by BYK Chemie) 20 Defoaming agent (manufactured by Shin-Etsu Chemical)

Table 2 Example 1 2 3 4 5 Evaluation item Storage stability △ ○ ○ △ ○ Resolution ○ ○ ○ ○ ○ Light sensitivity 12 11 10 10 12 Surface gloss ○ ○ ○ ○ ○ Adhesion ○ ○ ○ ○ ○ Pencil hardness 6H 7H 8H 4H 4H Solvent resistance ○ ○ ○ ○ ○ Acid resistance ○ ○ ○ ○ ○ Heat resistance ○ ○ ○ ○ ○ Gold plating resistance ○ ○ ○ ○ ○ PCT resistance ○ ○ ○ ○ ○ Thermal shock resistance ○ ○ ○ ○ ○

Example 6 A photosensitive resin composition was obtained by using the same composition except that the solvent for concentration adjustment in Example 4 was changed to methyl ethyl ketone and kneading with a bead mill to uniformly disperse.

The composition obtained was subjected to a roll coating method,
It is evenly applied to a polyethylene terephthalate film to be a support film, passed through a hot air drying oven at a temperature of 70 ° C. to form a resin layer having a thickness of 30 μm, and then a polyethylene film to be a protective film is attached onto the resin layer, A dry film was obtained. The obtained dry film was applied to a polyimide printed circuit board (copper circuit thickness: 12 μm / polyimide film thickness: 25 μm) using a heating roll at a temperature of 80 ° C. while the protective film was peeled off, and the resin layer was attached to the entire surface of the substrate.

Next, ultraviolet rays were irradiated (irradiation amount 500 mJ / square centimeter) using an ultraviolet reduction projection exposure apparatus equipped with a negative mask having an optical waveguide pattern. After irradiation, the support film was peeled off from the resin,
It was developed with a 5% tetramethylammonium aqueous solution for 30 seconds to dissolve and remove the unirradiated portion. After washing with water and drying, the printed board was subjected to a heat curing reaction for 30 minutes in a hot air dryer at 150 ° C. to obtain a cured film. The resulting cured product has good transparency and is 5
A 0 μm pattern was resolved.

Comparative Example A storage stability test was conducted with the same composition except that the curing catalyst (E) in Example 1 was changed to melamine. As a result, after 72 hours, development could not be performed at all.

As is clear from the above results, the photosensitive resin composition of the present invention is excellent in storage stability, developability, electrical insulation, adhesion, solder heat resistance, chemical resistance, gold plating resistance and the like. It is obvious that it is a photosensitive resin composition for a printed circuit board which gives a cured film.

[0062]

The photosensitive resin composition and its cured product are
It has excellent photosensitivity in the formation of coating film by exposure and curing with ultraviolet rays, and the cured product obtained has storage stability, developability, electrical insulation, adhesion, solder heat resistance, chemical resistance, gold plating resistance. Etc. are also sufficiently satisfied, and are particularly suitable for a one-pack type photosensitive resin composition for printed wiring boards, a dry film and a photosensitive resin composition for forming an optical waveguide.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05K 3/46 H05K 3/46 TF term (reference) 2H025 AA04 AA11 AA14 AA20 AB15 AC01 AD01 BC13 BC74 BC85 BC86 BD10 CA00 CB43 CB51 CC20 FA17 5E314 AA27 AA32 CC02 CC07 CC15 DD06 DD07 GG10 GG11 GG14 5E343 AA18 CC63 CC65 CC67 ER12 ER13 ER14 ER16 ER18 GG03 GG16 5E346 AA12 CC09 DD02 DD03 HH11 HH13 HH18

Claims (13)

[Claims] 1. A photosensitive resin composition containing an alkali aqueous solution soluble resin (A), a photopolymerization initiator (B), a photocrosslinking agent (C), a thermosetting component (D) and a curing catalyst (E).
The curing catalyst (E) may have an N-substituent, 1,
A photosensitive resin composition, which is a compound having a 4-dihydropyridine skeleton. 2. The curing catalyst (E) is a compound having a 4- (2′-nitrophenyl) -1,4-dihydropyridine skeleton, which may have an N-substituent. The photosensitive resin composition of. 3. The photosensitive resin composition according to claim 1, wherein the curing catalyst (E) is a compound represented by the following formula (1). [Chemical 1] (In the formula, R ₁ , R ₂ , R ₃ , and R ₄ represent a hydrogen atom, a halogen atom, a nitro group, or an alkyl group having 1 to 3 carbon atoms, and R ₅ , R ₆ are a nitrile group, -COOR. _{1 0} or indicates _{-COR 11,, R 7, R} 8 represents a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms, _{R 9} is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or aryl, Represents a group, and R ₁₀ and R ₁₁ represent a hydrogen atom or a carbon number of 1 to 3.
Is an alkyl group. ) 4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the alkaline aqueous solution-soluble resin (A) is a compound having a carboxyl group in the molecule. 5. An alkaline aqueous solution-soluble resin (A) comprises an epoxy compound (a) having two or more epoxy groups in the molecule and a monocarboxylic acid compound (c) having an unsaturated double bond in the molecule. The photosensitive resin composition according to any one of claims 1 to 4, which is a reaction product of an epoxycarboxylate compound obtained by the reaction with a polybasic acid anhydride (d). 6. The epoxy equivalent of the epoxy compound (a) having two or more epoxy groups in the molecule is 90 to 600 g.
6. The photosensitive resin composition according to any one of claims 1 to 5, which is an epoxy compound in an equivalent range. 7. A monocarboxylic acid compound (c) having an unsaturated double bond in the molecule is (meth) acrylic acid or (meth).
The monocarboxylic acid selected from the group consisting of a reaction product of acrylic acid and ε-caprolactone or a cinnamic acid group, or a monocarboxylic acid selected from the group consisting of two or more kinds. Photosensitive resin composition. 8. A polybasic acid anhydride (d) is succinic anhydride,
From the group of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride The photosensitive resin composition according to claim 1, wherein one kind or two or more kinds is selected. 9. The photosensitive resin composition according to any one of claims 1 to 8, wherein the solid content acid value of the aqueous alkaline solution-soluble resin (A) is in the range of 30 to 150 mg · KOH / g. . 10. A film coated with the photosensitive resin composition according to any one of claims 1 to 9. 11. A cured product of the photosensitive resin composition according to any one of claims 1 to 10. 12. A substrate having a layer of the cured product according to claim 11. 13. An article having the substrate according to claim 12.