JP2013228758A - Photocurable resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable resin composition having excellent adhesion with a substrate and excellent resolution; a film obtained by using the photocurable resin composition; a cured product obtained by curing the photocurable resin composition; and a printed wiring board comprising the cured product.SOLUTION: The photocurable resin composition is characterized by comprising (A) a carboxyl group-containing resin, (B) an acylphosphine oxide-based photopolymerization initiator, (C) a titanocene-based photopolymerization initiator, (D) a photosensitive monomer and (E) a polymerization inhibitor. The carboxyl group-containing resin contains at least any one kind of (A-1) to (A-10).

Description

  The present invention relates to a photocurable resin composition, a dry film, a cured product, and a printed wiring board.

  In recent years, as an insulating material such as a solder resist for consumer printed wiring boards and industrial printed wiring boards, from the viewpoint of high accuracy and high density, images are formed by developing after ultraviolet irradiation, and at least either heat or light irradiation. On the other hand, a liquid development type curable resin composition that undergoes final curing (main curing) is used.

  Among the liquid development type curable resin compositions, an alkali development type photocurable resin composition using an aqueous alkali solution as a developer is mainly used from the viewpoint of environmental problems. As such an alkali-developable photocurable resin composition, a composition mainly composed of an epoxy acrylate-modified resin derived by modification of an epoxy resin is generally used.

  For example, Patent Document 1 discloses a solder resist composition comprising a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak-type epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a diluent, and an epoxy compound. It is disclosed. In Patent Document 2, (meth) acrylic acid is added to an epoxy resin obtained by reacting a reaction product of salicylaldehyde with a monohydric phenol with epichlorohydrin, and a polybasic carboxylic acid or anhydride thereof is further added. A solder resist composition comprising a photosensitive resin obtained by reacting a product, a photopolymerization initiator, an organic solvent and the like is disclosed.

  Moreover, in order to cope with the increase in the density of printed wiring boards accompanying the reduction in thickness and size of electronic equipment, there is a demand for improved workability and higher performance of the curable resin composition. In recent years, the fine patterning of the wiring on the substrate has progressed, and L / S = 10 μm / 10 μm or less has been seen, and the solder resist is required to have a performance that can cope with such a fine pattern. Yes.

JP 61-243869 (Claims) Japanese Patent Laid-Open No. 3-250012 (Claims)

  In the fine pitch wiring pattern as described above, the influence of the unevenness of the substrate surface appears more greatly, and the wiring pattern does not stand upright on the rough surface, or the root of the wiring pattern is removed by etching and the pattern collapses Sometimes. Therefore, when a fine pitch wiring pattern is formed on a substrate, a substrate having a smooth surface is preferably used to ensure the stability of the wiring pattern.

  However, when an insulating layer such as a solder resist is formed on a base material having a smooth surface, the adhesion between the base material and the insulating layer is poor, and the state where the insulating layer is peeled off may occur. There was a problem that there was. In addition, high resolution is required for an insulating layer such as a solder resist so that the wiring can be made into a fine pattern.

  Accordingly, an object of the present invention is to provide a photocurable resin composition excellent in adhesion and resolution to a substrate, a film using the same, a cured product obtained by curing the photocurable resin composition, It is providing the printed wiring board provided with hardened | cured material.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a photocurable resin composition containing a titanocene-based photopolymerization initiator, which is excellent in resolution and adhesion to a substrate, and is smooth. The present inventors have found that even if the insulating layer is formed by coating on a substrate having a smooth surface, the occurrence of peeling and floating can be suppressed. However, since the titanocene photopolymerization initiator exhibits absorption / reactivity with respect to visible light, a photopolymerizable resin composition containing only a titanocene photopolymerization initiator as a photopolymerization initiator is poor in stability and short. There was a problem that the polymerization reaction started even under the irradiation of a yellow lamp whose wavelength was cut. As a result of further investigations, the present inventors have used a titanocene-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and a polymerization inhibitor in combination with the above-mentioned problems, so that the stability in the working environment is improved. The present inventors have found that the problem of sex can be solved and have completed the present invention.

  That is, the photocurable resin composition of the present invention comprises (A) a carboxyl group-containing resin, (B) an acylphosphine oxide photopolymerization initiator, (C) a titanocene photopolymerization initiator, (D) a photosensitive monomer, And (E) a polymerization inhibitor, and the (A) carboxyl group-containing resin is obtained by reacting (A-1) a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide. A carboxyl group-containing photosensitive resin obtained by reacting a product with an unsaturated group-containing monocarboxylic acid and reacting the resulting reaction product with a polybasic acid anhydride, (A-2) a bifunctional or higher polyfunctional A carboxyl group-containing photosensitive resin obtained by reacting a (solid) epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group present in the side chain, (A-3) a bifunctional (solid) epoxy A carboxyl group-containing photosensitive resin in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of the resin with epichlorohydrin, and a dibasic acid anhydride is added to the resulting hydroxyl group, (A -4) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound is reacted with an unsaturated group-containing monocarboxylic acid, and the resulting reaction product is a polybasic acid. Carboxyl group-containing photosensitive resin obtained by reacting anhydride, (A-5) diisocyanate, (meth) acrylate of bifunctional epoxy resin or its partially acid anhydride modified product, carboxyl group-containing dialcohol compound and diol compound Carboxyl group-containing photosensitive urethane resin by polyaddition reaction of (A-6) diisocyanate and carbo Carboxyl group-containing non-photosensitive urethane resin by polyaddition reaction of sil group-containing dialcohol compound and polyol or diol compound, (A-7) Bifunctional oxetane resin is reacted with dicarboxylic acid, and the resulting primary hydroxyl group has two bases A carboxyl group-containing non-photosensitive polyester resin to which an acid anhydride is added, (A-8) During the synthesis of the resin of (A-5) or (A-6), one hydroxyl group and one or more in the molecule During the synthesis of the carboxyl group-containing photosensitive urethane resin (A-9) or the resin (A-5) or (A-6), which was added with a compound having a (meth) acryloyl group. , A carboxyl group-containing photosensitive urethane obtained by adding a compound having one isocyanate group and one or more (meth) acryloyl groups in the molecule and terminally (meth) acrylating the compound Resin, (A-10) A carboxyl obtained by adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule to the resins (A-1) to (A-9). It contains at least any one of group-containing photosensitive resins.

In the photocurable resin composition of the present invention, the (B) acylphosphine oxide photopolymerization initiator is preferably a compound having a partial structure represented by the following general formula (I).
Wherein R ¹ and R ² are each independently a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms. , An aryl group having 6 to 20 carbon atoms which may be substituted with at least any one of a cycloalkyl group having 5 to 20 carbon atoms, an alkyl group and an alkoxy group, or at least one of an alkyl group and an alkoxy group Or an arylcarbonyl group having 7 to 20 carbon atoms which may be substituted with one kind.)

In the photocurable resin composition of the present invention, the (C) titanocene photopolymerization initiator is preferably a compound represented by the following general formula (II).
Wherein R ³ and R ⁴ are each independently substituted with one or more substituents selected from a halogen atom, an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkoxyalkylcarbonyl group, an aryl group and a heterocyclic group. Represents an optionally substituted aryl group having 6 to 20 carbon atoms.)

In the photocurable resin composition of the present invention, the (C) titanocene photopolymerization initiator is preferably a compound represented by the following formula.

  In the photocurable resin composition of the present invention, the (E) polymerization inhibitor preferably contains at least one of a naphthalene derivative, a naphthoquinone, and a naphthoquinone derivative.

  In the photocurable resin composition of the present invention, the (A) carboxyl group-containing resin preferably contains a carboxyl group-containing resin obtained using a phenol compound as a starting material.

  The dry film of the present invention is obtained by coating and drying any one of the above photocurable resin compositions on a film.

  The cured product of the present invention is obtained by curing any one of the above photocurable resin compositions or the above dry film.

  The printed wiring board of the present invention comprises the above cured product.

  According to the present invention, a photocurable resin composition having excellent adhesion and resolution to a substrate and having stability and HAST resistance in a work environment, a film using the same, and the photocuring It becomes possible to provide a cured product obtained by curing the conductive resin composition and a printed wiring board provided with the cured product.

It is a photograph figure showing the state without peeling in the adhesive evaluation of an Example. It is a photograph figure showing the state with peeling in the adhesive evaluation of an Example.

The photocurable resin composition of the present invention comprises (A) a carboxyl group-containing resin, (B) an acylphosphine oxide photopolymerization initiator, (C) a titanocene photopolymerization initiator, (D) a photosensitive monomer, and ( E) It contains a polymerization inhibitor. By setting it as the above structures, it can be set as the photocurable resin composition which was excellent in the adhesiveness and resolution with respect to a base material, and was provided with stability in a working environment. Here, the stability in the working environment is a property that the curing reaction does not proceed or the progress of the curing reaction is suppressed in the state where the exposure is not performed with ultraviolet rays under the irradiation of a yellow lamp with a short wavelength cut. is there.
Hereinafter, each component will be described in detail.

[(A) Carboxyl group-containing resin]
In the present invention, (A) various conventionally known carboxyl group-containing resins having a carboxyl group in the molecule can be used as the (A) carboxyl group-containing resin, and in particular, it has an ethylenically unsaturated double bond in the molecule. A carboxyl group-containing photosensitive resin is preferred from the viewpoints of photocurability and resolution. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof.
Specific examples of the carboxyl group-containing resin include the following compounds (any of oligomers and polymers).

  (1) Reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.

  (2) Carboxyl group-containing photosensitivity in which (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin as described later and a dibasic acid anhydride is added to the hydroxyl group present in the side chain. Resin.

  (3) A polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. Added carboxyl group-containing photosensitive resin.

  (4) Obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a reaction product obtained by reacting a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

  (5) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by polyaddition reaction of (meth) acrylate or a partially acid anhydride modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

  (6) Non-photosensitive carboxyl group obtained by copolymerization of unsaturated carboxylic acid such as (meth) acrylic acid and unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate and isobutylene Resin.

  (7) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers Carboxyl group-containing non-photosensitive property by polyaddition reaction of diol compounds such as polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups Urethane resin.

  (8) A dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid is reacted with a bifunctional oxetane resin as described later, and the resulting primary hydroxyl group is phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride. A carboxyl group-containing non-photosensitive polyester resin to which a dibasic acid anhydride such as

  (9) During the synthesis of the resin of the above (5) or (7), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing photosensitive urethane resin.

  (10) During the synthesis of the resin of (5) or (7) above, one isocyanate group and one or more (meth) acryloyl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal (meth) acrylate.

(11) A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule to the resins (1) to (10).
In addition, in this specification, (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

Since the carboxyl group-containing resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
The acid value of the carboxyl group-containing resin is suitably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary. Depending on the case, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.

  Moreover, although the weight average molecular weight of the said carboxyl group containing resin changes with resin frame | skeletons, what is generally in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

  The amount of such a carboxyl group-containing resin is 20 to 60% by mass, preferably 30 to 50% by mass in the entire composition. When the amount of the carboxyl group-containing resin is less than the above range, the coating strength is lowered, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity of the composition is increased or the coating property is lowered, which is not preferable.

  These carboxyl group-containing resins are not limited to those listed above, and one kind thereof may be used alone, or a plurality of kinds may be used in combination. In particular, among the carboxyl group-containing resins, resins having an aromatic ring are preferable because they have a high refractive index and excellent resolution, and those having a novolak structure not only have resolution but also PCT and It is preferable because of excellent crack resistance. Among them, the carboxyl group-containing photosensitive resins (1) and (2) are preferable because a solder resist having excellent resolution can be obtained while satisfying various properties such as PCT resistance.

[(B) Acylphosphine oxide photopolymerization initiator]
The (B) acylphosphine oxide photopolymerization initiator may be any acylphosphine oxide photopolymerization initiator known as a photopolymerization initiator or photoradical generator. Specific examples include (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine. Oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, bis ( 2,6-dimethoxybenzoyl) phenylphosphine oxide, ethyl-2,4,6-trimethylbenzoylphenylphosphinate and the like. Examples of commercially available products include Lucilin TPO, Lucillin TPO-L, LR8953X, Irgacure 819, and Irgacure 1700 manufactured by BASF.

As the (B) acylphosphine oxide photopolymerization initiator, an acylphosphine oxide photopolymerization initiator having a group represented by the following general formula (I) is preferable.
Wherein R ¹ and R ² are each independently a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms. , An aryl group having 6 to 20 carbon atoms which may be substituted with at least any one of a cycloalkyl group having 5 to 20 carbon atoms, an alkyl group and an alkoxy group, or at least one of an alkyl group and an alkoxy group Or an arylcarbonyl group having 7 to 20 carbon atoms which may be substituted with one kind.)

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, and hexyl groups. Examples of the linear or branched alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group. Examples of the cycloalkyl group having 5 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group, and those in which these cycloalkyl groups are substituted with an alkyl group, an alkoxy group, or the like. Examples of the aryl group having 6 to 20 carbon atoms which may be substituted with at least one of the alkyl group and the alkoxy group include a phenyl group, a naphthyl group, and an aryl group such as an alkyl group and an alkoxy group. The thing substituted by at least any 1 type is mentioned. The arylcarbonyl group having 7 to 20 carbon atoms which may be substituted with at least one of the above alkyl group and alkoxy group is A- (C = O)-(A is the alkyl group or alkoxy group. Represents an aryl group which may be substituted with at least one of them, and specific examples include a benzyl group and a trimethylbenzyl group.

  The (B) acylphosphine oxide photopolymerization initiator may be used alone or in combination of two or more. The content of the (B) acylphosphine oxide photopolymerization initiator in the photocurable resin composition of the present invention is preferably 0.5 to 50 with respect to 100 parts by mass of the (A) carboxyl group-containing resin. It is a mass part, More preferably, it is 1-30 mass parts.

[(C) titanocene photopolymerization initiator]
As the (C) titanocene photopolymerization initiator, any known photopolymerization initiator having a titanocene structure and capable of being sensitive at a light absorption wavelength of 400 to 700 nm can be used. Specific examples of the titanocene photopolymerization initiator include, for example, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (1-pyr-1-yl) ethyl) phenyl] titanium, Bis (cyclopentadienyl) -bis [2,6-difluoro-3- (3- (1-pyr-1-yl) propyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6- Difluoro-3-((1-pyr-1-yl) methyl) phenyl] titanium, bis (methylcyclopentadienyl) -bis [2,6-difluoro-3-((1-pyr-1-yl) methyl ) Phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-((2,5-dimethyl-1-pyr-1-yl) methyl) phenyl] titanium, bis (cyclo Ntadienyl) -bis [2,6-difluoro-3-((2-isopropyl-5-methyl-1-pyr-1,6-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2 , 6-Difluoro-3-((2- (2-methoxyethyl) -5-methyl-1-pyr-1-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6- Difluoro-3-((3-trimethylsilyl-2,5-dimethyl-1-pyr-1-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-(( 2,5-dimethyl-3- (bis (2-methoxyethyl) aminomethyl) -1-pyr-1-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6 Difluoro-3-((2,5-bis (morpholinomethyl) -1-pyr-1-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-(( 2,5-dimethyl-3- (1,3-dioxolan-2-yl) -1-pyr-1-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro- 4-((2,5-dimethyl-1-pyr-1-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-methyl-4- (2- ( 1-pyr-1-yl) ethyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-((2,3,4,5-tetramethyl-1-pyr-1) -Yl) methyl) pheny Ru] titanium, bis (cyclopentadienyl) -bis [2,3,5,6-tetrafluoro-4- (3- (1-pyr-1-yl) propyl) phenyl] titanium, bis (cyclopentadi) Enyl) -bis [2,6-difluoro-3- (2- (1-pyr-1-yl) propyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- ( 1-methyl-2- (1-pyr-1-yl) ethyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (3- (2-isoindol-2-yl) ) Propyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (4,5,6,7-tetrahydro-isoindol-2-yl) ethyl) phenyl] Titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (6- (9-carbazol-9-yl) hexyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2, 6-Difluoro-3- (3- (2,3,4,5,6,7,8,9-octahydro-1-carbazol-9-yl) propyl) phenyl] titanium, bis (cyclopentadienyl)- Bis [2,6-difluoro-3- (3- (4,5,6,7-tetrahydro-2-methyl-1-indol-1-yl) propyl) phenyl] titanium, bis (cyclopentadienyl)- Bis [2,6-difluoro-3-((acetylamino) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (propionyl) Mino) ethyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (3- (acetylamino) propyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2 , 6-Difluoro-3- (4- (bivaloylamino) butyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (2,2-dimethylpentanoyl) Amino) ethyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (3- (benzoylamino) propyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2 , 6-Difluoro-3-((2,2-dimethylpentanoylamino) methyl) phenyl] titanium, bis (cyclopent Tadienyl) -bis [2,6-difluoro-3- (2- (2,2-dimethyl-3-chloropropanoylamino) ethyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6- Difluoro-3-((2,2-dimethyl-3-ethoxypropanoylamino) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (lauroylamino) Ethyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (N-allylmethylsulfonylamino) ethyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (3- (N-isobutylphenylsulfonylamino) propyl) phenyl] titanium, bis Cyclopentadienyl) -bis [2,6-difluoro-3-((methylsulfonylamino) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (3- ( Ethylsulfonylamino) propyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (butylsulfonylamino) ethyl) phenyl] titanium, bis (cyclopentadienyl)- Bis [2,6-difluoro-3- (4- (trisulfonylamino) propyl) phenyl] titanium, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3 -(1H-pyrrol-1-yl) phenyl) titanium and the like. These titanocene photopolymerization initiators can be used alone or in combination of two or more. Examples of commercially available products include Irgacure-784 manufactured by BASF Japan.

  Further, as the (C) titanocene photopolymerization initiator, a compound represented by the following general formula (II) is preferable, and a compound represented by the following general formula (III) is more preferable.

Wherein R ³ and R ⁴ are each independently substituted with one or more substituents selected from a halogen atom, an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkoxyalkylcarbonyl group, an aryl group and a heterocyclic group. Represents an optionally substituted aryl group having 6 to 20 carbon atoms.)

(Wherein R ⁵ and R ⁶ are each independently a linear or branched alkylcarbonyl group having 2 to 14 carbon atoms, an alkoxyalkylcarbonyl group having 3 to 14 carbon atoms, or nitrogen as a hetero atom) (Represents a 5-membered or 6-membered heterocyclic group having an atom, sulfur atom or oxygen atom.)

  Examples of the halogen atom, alkyl group, alkoxy group, and aryl group are the same as those described above. The alkylcarbonyl group is a group in which the above-described alkyl group is bonded to a carbonyl group. The alkoxyalkylcarbonyl group is obtained by bonding an alkyl group substituted with an alkoxy group to a carbonyl group. Examples of the 5- or 6-membered heterocyclic group having a nitrogen atom, sulfur atom or oxygen atom as a hetero atom include pyrrolidine, tetrahydrofuran, tetrahydrothiophene, pyrrole, furan, thiophene, piperidine, tetrahydropyran, pyridine and the like. .

As the (C) titanocene photopolymerization initiator, a compound represented by the following formula is particularly preferable.

The said titanocene type photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type. As content of (C) titanocene photoinitiator in the photocurable resin composition of this invention, Preferably it is 0.01-10 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin. Yes, more preferably 0.01 to 8 parts by mass.
A suitable ratio of (B) :( C) is 1: 0.01 to 1: 1, more preferably 1: 0.01 to 1: 0.5.

[(D) Photosensitive monomer]
(D) The photosensitive monomer is a compound having an ethylenically unsaturated group in the molecule, and is used for adjusting the viscosity of the photocurable resin composition, promoting photocurability and improving developability. As such a compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate can be used, Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide , N-methylolacrylamide, N, N-dimethylaminopropylacrylamide and other acrylamides; N, N-dimethylaminoethyl acrylate, N Aminoalkyl acrylates such as N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethylisocyanurate, or their ethylene oxide adducts, propylene oxide adducts Or polyhydric acrylates such as ε-caprolactone adduct; polyhydric acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adduct or propylene oxide adduct of these phenols; glycerin diglycidyl ether, glycerin Triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc. Polyacid acrylates of sidyl ether; not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates, And at least one of the methacrylates corresponding to the acrylate.

  Furthermore, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. The epoxy urethane acrylate compound etc. which made the half urethane compound react are mentioned. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  A compound having an ethylenically unsaturated group in the molecule as described above may be used alone or in combination of two or more. In particular, a compound having 4 to 6 ethylenically unsaturated groups in one molecule is preferable from the viewpoint of photoreactivity and resolution, and a compound having two ethylenically unsaturated groups in one molecule is used. And the linear thermal expansion coefficient of hardened | cured material falls and it is preferable from generation | occurrence | production of peeling at the time of PCT being reduced.

  As for the compounding quantity of the compound which has an ethylenically unsaturated group in the above molecules, 5-100 mass parts is preferable with respect to 100 mass parts of said (A) carboxyl group-containing resin. When the blending amount is less than 5 parts by mass, the photocurability is lowered, and pattern formation may be difficult due to alkali development after irradiation with active energy rays. On the other hand, when it exceeds 100 mass parts, the solubility with respect to dilute alkali aqueous solution may fall, and a coating film may become weak. More preferably, it is 1-70 mass parts.

[(E) Polymerization inhibitor]
In order to improve the storage stability of the composition, it is preferable to add (E) a polymerization inhibitor to the photocurable resin composition of the present invention. (E) As the polymerization inhibitor, a conventionally known (thermal) polymerization inhibitor can be used. (E) As a polymerization inhibitor, for example, phenothiazine, hydroquinone, N-phenylnaphthylamine, chloranil, pyrogallol, benzoquinone, t-butylcatechol, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, naphthoquinone or naphthoquinone derivatives such as 4-methoxy-1-naphthol, 2-hydroxy 1,4-naphthoquinone, etc., among which naphthoquinone or naphthoquinone derivatives are preferred.

  The said polymerization inhibitor may be used individually by 1 type, and may be used in combination of 2 or more type. As content of the polymerization inhibitor in the photocurable resin composition of this invention, Preferably it is 0.01-5 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin, More preferably, it is 0. 0.05 to 3 parts by mass.

(Other photopolymerization initiators)
The photocurable resin composition of the present invention may contain a photopolymerization initiator other than the above-described acylphosphine oxide photopolymerization initiator and titanocene photopolymerization initiator as long as the effect is not inhibited. Examples of such photopolymerization initiators include oxime ester photopolymerization initiators having an oxime ester group, alkylphenone photopolymerization initiators, and α-aminoacetophenone photopolymerization initiators.

  In particular, the oxime ester-based initiator may be added in a small amount, and outgassing is suppressed, which is preferable because it is effective in PCT resistance and crack resistance.

Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, NCI-831 manufactured by ADEKA, and the like as commercially available products. Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.
(In the formula, X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, 1 carbon atom) -8 alkoxy groups, amino groups, substituted with alkylamino groups or dialkylamino groups having an alkyl group having 1 to 8 carbon atoms, naphthyl groups (alkyl groups having 1 to 17 carbon atoms, carbon atoms) 1-8 alkoxy group, amino group, alkylamino group having 1-8 carbon atoms alkyl group or dialkylamino group), Y and Z are each a hydrogen atom, 1 carbon atom. -17 alkyl group, alkoxy group having 1 to 8 carbon atoms, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, A mino group, substituted with an alkylamino group or dialkylamino group having an alkyl group having 1 to 8 carbon atoms, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms) An anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, Ar is a bond, or an amino group, substituted with an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group) C1-C10 alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-stilbene-diyl, 4,2'-styrene -Represented by diyl, n is an integer of 0 or 1.

  In particular, in the above general formula, X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, and Ar is a bond, phenylene, naphthylene, thiophene or thienylene. It is preferable.

Moreover, the compound which can be represented by the following general formula can also be mentioned as a preferable carbazole oxime ester compound.
(In the formula, R ¹ represents an alkyl group or a nitro group, a halogen atom or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.
R ² represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group.
R ³ may be linked with an oxygen atom or a sulfur atom, and may be substituted with an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 4 carbon atoms which may be substituted with a phenyl group. Represents a good benzyl group.
R ⁴ represents a nitro group or an acyl group represented by X—C (═O) —.
X represents an aryl group, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula, which may be substituted with an alkyl group having 1 to 4 carbon atoms. )

  In addition, JP-A-2004-359639, JP-A-2005-097141, JP-A-2005-220097, JP-A-2006-160634, JP-A-2008-094770, JP-A-2008-509967, Specific examples include carbazole oxime ester compounds described in JP2009-040762A and JP2011-80036A.

  Examples of commercially available alkylphenone photopolymerization initiators include α-hydroxyalkylphenone types such as Irgacure 184, Darocur 1173, Irgacure 2959, and Irgacure 127 manufactured by BASF Japan.

  As the α-aminoacetophenone photopolymerization initiator, specifically, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by BASF Japan.

  In addition, Irgacure 389 manufactured by BASF Japan can be suitably used as a photopolymerization initiator.

(Photoinitiator aid, sensitizer)
As long as the effect is not inhibited, the photocurable resin composition of the present invention can use a photoinitiator auxiliary agent and a sensitizer in addition to the photopolymerization initiator. Examples of the photoinitiation assistant and sensitizer that can be suitably used include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds.

  Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.

  Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, and the like.

  Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

  Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.

  Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyldiphenyl. And sulfides.

  Specifically, as the tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, for example, 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), Dialkylaminobenzophenone such as 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4- Dialkylamino group-containing coumarin compounds such as methylcoumarin), ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics) 4 Dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamylethyl ester (Nippon Kayaku Co., Ltd. Kayacure DMBI), 4-dimethylaminobenzoic acid Examples thereof include 2-ethylhexyl (Esolol 507 manufactured by Van Dyk), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), and the like.

  Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, the inclusion of a thioxanthone compound is preferable from the viewpoint of deep curability. Among them, it is preferable to include a thioxanthone compound such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

  As a compounding quantity of such a thioxanthone compound, it is preferable that it is 20 mass parts or less with respect to 100 mass parts of said carboxyl group-containing resin. When the blending amount of the thioxanthone compound exceeds 20 parts by mass, the thick film curability is lowered and the cost of the product is increased. More preferably, it is 10 parts by mass or less.

  As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength in the range of 350 to 450 nm, and ketocoumarins are particularly preferable. .

  As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. The dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm in the ultraviolet region, so it is less colored and uses not only a colorless and transparent photocurable composition but also a colored pigment, which reflects the color of the colored pigment itself. A colored solder resist can be provided. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  As a compounding quantity of such a tertiary amine compound, it is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of said (A) carboxyl group-containing resin. When the amount of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. On the other hand, when the amount exceeds 20 parts by mass, light absorption on the surface of the dried solder resist by the tertiary amine compound becomes intense, and the deep curability tends to decrease. More preferably, it is 0.1-10 mass parts.

These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.
The total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the (A) carboxyl group-containing resin. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  A thermosetting component can be added to the photocurable resin composition of the present invention. It can be expected that heat resistance is improved by adding a thermosetting component. Examples of thermosetting components used in the present invention include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, benzoguanamine derivatives, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, bismaleimides. Well-known thermosetting resins such as carbodiimide resins can be used. Particularly preferred is a thermosetting component having at least one of a plurality of cyclic ether groups and cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.

  The thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is a compound having any one of the three, four or five-membered cyclic (thio) ether groups in the molecule or a plurality of two types of groups. For example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, That is, episulfide resin etc. are mentioned.

  Examples of the polyfunctional epoxy compound include epoxidized vegetable oils such as Adekasizer O-130P, Adekasizer O-180A, Adekasizer D-32, and Adekasizer D-55 manufactured by ADEKA; jER828 and jER834 manufactured by Mitsubishi Chemical Corporation; jER1001, jER1004, EHPE3150 manufactured by Daicel Chemical Industries, Epicron 840, Epicron 850, Epicron 1050, Epicron 1050, Epicron 2055, Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Tohto Kasei Co., Ltd. D. Chemicals manufactured by Dow Chemical Company. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumitomo Epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. 664phenol (all trade names) bisphenol A type epoxy resin; YDC-1312, hydroquinone type epoxy resin, YSLV-80XY bisphenol type epoxy resin, YSLV-120TE thioether type epoxy resin (all manufactured by Tohto Kasei Co., Ltd.); JERYL903 manufactured by DIC, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., D.C. E. R. 542, Sumitomo Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., EPPN-201, EOCN-1025, EOCN manufactured by Nippon Kayaku Co., Ltd. -1020, EOCN-104S, RE-306, Sumitomo Epoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Co., Ltd. E. R. Novolak type epoxy resins such as ECN-235 and ECN-299 (both are trade names); biphenol novolac type epoxy resins such as NC-3000 and NC-3100 manufactured by Nippon Kayaku; Epicron 830 manufactured by DIC, Mitsubishi Chemical JER807 manufactured by Toto Kasei Co., Ltd. Etototo YDF-170, YDF-175, YDF-2004, etc. (all trade names) bisphenol F type epoxy resin; Toto Kasei Co., Ltd. Epototo ST-2004, ST-2007, ST- Hydrogenated bisphenol A type epoxy resin such as 3000 (trade name); jER604 manufactured by Mitsubishi Chemical Co., Ltd., Epotot YH-434 manufactured by Tohto Kasei Co., Ltd., Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. ) Glycidylamine type epoxy resin; hydantoin type epoxy resin; Alicyclic epoxy resins GMBH made CELLOXIDE 2021, etc. (all trade names); manufactured by Mitsubishi Chemical Corporation YL-933, Dow Chemical Co. of T. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names) Type or biphenol type epoxy resin or a mixture thereof; Nippon Kayaku EBPS-200, ADEKA EPX-30, DIC EXA-1514 (trade name), etc .; bisphenol S type epoxy resin; Bisphenol A novolac type epoxy resin such as jER157S (trade name); tetraphenylolethane type epoxy resin such as jERYL-931 (all trade name) made by Mitsubishi Chemical; TEPIC made by Nissan Chemical Industries (all) Product name) heterocyclic epoxy resin; Jig such as Bremer DGT manufactured by NOF Corporation Shidyl phthalate resin; Tetraglycidyl xylenoyl ethane resin such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. HP-4032, EXA-4750, EXA-4700 manufactured by DIC Naphthalene group-containing epoxy resin; epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by NOF Corporation; Further, a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; an epoxy-modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industries), a CTBN-modified epoxy resin (for example, YR-102, YR-450 manufactured by Toto Kasei Co., Ltd.) ) Etc. That is, the present invention is not limited to these. These epoxy resins can be used alone or in combination of two or more. Among these, novolak-type epoxy resins, bixylenol-type epoxy resins, biphenol-type epoxy resins, biphenol novolac-type epoxy resins, naphthalene-type epoxy resins or mixtures thereof are particularly preferable.

  Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3- Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3- In addition to polyfunctional oxetanes such as oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin , Poly (p-hydroxystyrene), cardo-type bis Phenol ethers, calixarenes, calix resorcin arenes or etherified products such as the resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

  The blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in such a molecule is 0.6 to 2.5 equivalents relative to 1 equivalent of the carboxyl group of the (A) carboxyl group-containing resin. preferable. When the blending amount is less than 0.6, a carboxyl group remains in the cured product, and heat resistance, alkali resistance, electrical insulation, and the like are lowered. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, thereby reducing the strength of the coating film. More preferably, it is 0.8-2.0 equivalent.

  Furthermore, examples of other thermosetting components include amino resins such as melamine derivatives and benzoguanamine derivatives. For example, there are methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.

  Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156. 1158, 1123, 1170, 1174, UFR65, 300 (all manufactured by Mitsui Cyanamid), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx- 290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw- 750LM (all manufactured by Sanwa Chemical Co., Ltd.). Such thermosetting components can be used alone or in combination of two or more.

  A compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be added to the photocurable resin composition of the present invention. Examples of such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule include polyisocyanate compounds or blocked isocyanate compounds. The blocked isocyanate group is a group in which the isocyanate group is protected by the reaction with the blocking agent and temporarily inactivated, and the blocking agent is dissociated when heated to a predetermined temperature. Produces. It was confirmed that the curability and toughness of the resulting cured product were improved by adding the polyisocyanate compound or the blocked isocyanate compound.

As such a polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
Specific examples of the aromatic polyisocyanate include, for example, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, Examples thereof include m-xylylene diisocyanate and 2,4-tolylene dimer.

  Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate.

  Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adducts, burettes and isocyanurates of the above-mentioned isocyanate compounds can be used.

  As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. As an isocyanate compound which can react with a blocking agent, the above-mentioned polyisocyanate compound etc. are mentioned, for example.

  Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, milk Alcohol-based blocking agents such as methyl and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine Etc.

  The block isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117. , Desmotherm 2170, Desmotherm 2265 (all manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate 2512, Coronate 2513, Coronate 2520 (all manufactured by Nippon Polyurethane Industry Co., Ltd.), B-830, B-815, B-846, B-870, B-874, B-882 (all manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (all manufactured by Asahi Kasei Chemicals Co., Ltd.) and the like. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent. Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule may be used alone or in combination of two or more.

  The compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. When the blending amount is less than 1 part by mass, sufficient coating film toughness cannot be obtained. On the other hand, when it exceeds 100 mass parts, storage stability falls. More preferably, it is 2-70 mass parts.

(Thermosetting catalyst)
When using the thermosetting component which has a some cyclic | annular (thio) ether group in a molecule | numerator, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, the present invention is not limited to these, and any epoxy resin or oxetane compound thermosetting catalyst or any one that promotes the reaction of a carboxyl group with at least one of an epoxy group and an oxetanyl group may be used alone or in combination. A mixture of seeds or more may be used. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with a thermosetting catalyst.

  The compounding amount of these thermosetting catalysts is sufficient in the usual quantitative ratio, for example, for 100 parts by mass of the (A) carboxyl group-containing resin or thermosetting component having a plurality of cyclic (thio) ether groups in the molecule. The amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.

(Inorganic filler)
The photocurable resin composition of the present invention preferably contains an inorganic filler. The inorganic filler is used for suppressing the curing shrinkage of the cured product of the photocurable resin composition and improving the properties such as adhesion and hardness. Examples of inorganic fillers include barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and nitriding Examples thereof include silicon and aluminum nitride.

  Moreover, it is preferable that the photocurable resin composition of this invention contains the filler which has a refractive index in the range of 1.50-1.65 further. In particular, the filler having a refractive index in the range of 1.50 to 1.65 preferably contains at least one of Ba, Mg, and Al.

  The average particle size of the inorganic filler is preferably 5 μm or less. The blending ratio is preferably 75% by mass or less, more preferably 0.1 to 60% by mass, based on the total solid content of the photocurable resin composition. When the blending ratio of the inorganic filler exceeds 75% by mass, the viscosity of the composition increases, and the applicability may decrease, or the cured product of the photocurable resin composition may become brittle.

(Elastomer)
An elastomer having a functional group can be added to the photocurable resin composition of the present invention. By adding an elastomer having a functional group, it is expected that the coating property is improved and the strength of the coating film is also improved. Examples of the elastomer having a functional group include R-45HT, Poly bd HTP-9 (manufactured by Idemitsu Kosan Co., Ltd.), Epolide PB3600 (manufactured by Daicel Chemical Industries, Ltd.), Denarex R-45EPT. (Manufactured by Nagase ChemteX Co., Ltd.), Ricon 130, Ricon 131, Ricon 134, Ricon 142, Ricon 150, Ricon 152, Ricon 153, Ricon 154, Ricon 156, Ricon 157, Ricon 100, Ricon 181, Ricon 181 130MA8, Ricon 130MA13, Ricon 130MA20, Ricon 131MA5, Ricon 131MA10, Ricon 131MA17, Ricon 131MA20, Ric n 184MA6, Ricon 156MA17 (manufactured by Sartomer Company, Inc.), and the like. Polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyesteramide elastomers, acrylic elastomers, and olefin elastomers can be used. In addition, resins in which some or all of the epoxy groups of epoxy resins having various skeletons are modified with carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used. Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers, and the like can also be used. The blending amount of these elastomers is preferably in the range of 3 to 124 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. Moreover, these elastomers may be used individually by 1 type, and may use 2 or more types together.

(Mercapto compound)
You may add a mercapto compound to the photocurable resin composition used by this invention as needed. By adding a mercapto compound, it can be expected that PCT resistance and HAST resistance are improved. This is thought to be due to improved adhesion.

  Examples of the mercapto compound include mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof such as 1-butanethiol, butyl-3-mercaptopropionate, methyl-3- Mercaptopropionate, 2,2- (ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanethiol, cyclohexanethiol , Thioglycerol, 4,4-thiobisbenzenethiol and the like.

  Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PMP, DPMP, and TEMPIC (above, manufactured by Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, And Karenz-NR1 (manufactured by Showa Denko KK).

Further, examples of the mercapto compound having a heterocyclic ring include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, and 2-mercapto-4-ethyl-4. -Butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam, N-methyl- 2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl-2-mercapto- 4-butyrolactam, 2-mercapto-5-valerolactone, 2-mer Pto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto-5-valerolactam N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2-mercaptobenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 2-mercapto-6-hexanolactam, 2,4,6 -Trimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name Disnet F), 2-dibutylamino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name Disnet DB) , And 2-anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name Disnet AF) and the like.
Among these, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (manufactured by Kawaguchi Chemical Co., Ltd .: trade name Accel M), 3-mercapto-4-methyl-4H-1,2, 4-Triazole, 5-methyl-1,3,4-thiadiazole-2-thiol and 1-phenyl-5-mercapto-1H-tetrazole are preferred.

  The blending amount of such a mercapto compound is suitably 0.01 parts by weight or more and 10.0 parts by weight or less, more preferably 0.05 parts by weight with respect to 100 parts by weight of the (A) carboxyl group-containing resin. Part to 5 parts by mass. If it is less than 0.01 part by mass, the improvement in adhesion as an effect of adding a mercapto compound is not confirmed. On the other hand, if it exceeds 10.0 parts by mass, the development failure of the photocurable resin composition and the decrease in the dry management width will be confirmed. This is not preferable because it may cause These mercapto compounds may be used alone or in combination of two or more.

(Coloring agent)
Furthermore, a colorant can be mix | blended with the photocurable resin composition of this invention. As the colorant, conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. Specific examples include those with the following color index numbers (CI; issued by The Society of Dyers and Colorists). However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.

Red colorant:
Examples of red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. It is done.
Monoazo: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.
Disazo: Pigment Red 37, 38, 41.
Monoazo lakes: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1, 68.
Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.
Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.
Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
Condensed azo series: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242.
Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.
Kinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:
Blue colorants include phthalocyanine-based and anthraquinone-based pigments, and pigment-based compounds such as Pigment Blue 15 and Pigment Blue 15 are listed below. : 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, and Pigment Blue 60.
The dye systems include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:
Similarly, green colorants include phthalocyanine, anthraquinone, and perylene. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5
Solvent Green 20, Solvent Green 28, etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:
Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
Isoindolinone type: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
Condensed azo series: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.
Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.
Monoazo: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183.
Disazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

In addition, a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone.
For example, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black And the like.

  The colorant as described above can be appropriately blended, but is preferably 10 parts by mass or less with respect to 100 parts by mass of the (A) carboxyl group-containing resin or thermosetting component. More preferably, it is 0.1-5 mass parts.

(Organic solvent)
Furthermore, the photocurable resin composition of the present invention uses an organic solvent for the synthesis of the carboxyl group-containing resin and the preparation of the composition, or for adjusting the viscosity for application to a substrate or a carrier film. Can do.
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such an organic solvent may be used individually by 1 type, and may be used 2 or more types as a mixture.

  The photo-curable resin composition of the present invention further contains an antioxidant such as a radical scavenger and a peroxide decomposer, an ultraviolet absorber, an adhesion promoter, fine silica, organic bentonite, and montmorillonite as necessary. At least one of defoamers and leveling agents such as adhesives, silicones, fluorines and polymers, silane coupling agents such as imidazole, thiazole and triazoles, rust inhibitors and flame retardants Such known additives can be blended.

  The photocurable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using, for example, the organic solvent, and on a substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method. A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (temporary drying). Further, in the case of a dry film obtained by applying the above composition on a carrier film and drying and winding up as a film, the photocurable resin composition layer was laminated on the base material by a laminator or the like so as to come into contact with the base material. Thereafter, the resin insulating layer can be formed by removing the carrier film.

  Examples of the base material include printed circuit boards and flexible printed circuit boards in which circuits are formed in advance, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber. Copper graded laminates of all grades (FR-4 etc.) and other polyimides using materials such as epoxy, fluorine, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate ester, etc. A film, a PET film, a glass substrate, a ceramic substrate, a wafer plate, etc. can be mentioned.

  Volatile drying performed after applying the photo-curable resin composition of the present invention is performed in a dryer using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (equipped with an air heating heat source using steam). The method can be carried out using a method in which hot air is brought into countercurrent contact and a method in which the hot air is blown onto the support.

  The exposed part (irradiated with active energy rays) was applied to the coating film obtained after applying the photo-curable resin composition of the present invention and evaporating and drying the solvent (irradiation with active energy rays). Part) is cured. Further, by a contact method (or a non-contact method), exposure is selectively performed with an active energy ray through a photomask having a pattern formed thereon or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3 The resist pattern is formed by development with a 3 wt% sodium carbonate aqueous solution.

As an exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, and the like may be used as long as the apparatus irradiates ultraviolet rays in a range of 350 to 450 nm. Furthermore, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can also be used. As a laser light source of the direct drawing machine, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. The amount of exposure for image formation varies depending on the film thickness and the like, but is generally 20 to 800 mJ / cm ² , preferably 20 to 600 mJ / cm ² .

  The developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.

The photocurable resin composition of the present invention is suitable as a permanent film for a printed wiring board, and particularly suitable as a solder resist or an interlayer insulating material.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples and comparative examples.

(Synthesis Example 1)
600 g of diethylene glycol monoethyl ether acetate, 1070 g of orthocresol novolac type epoxy resin (manufactured by DIC, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6), 360 g of acrylic acid, and 1.5 g of hydroquinone Was heated and stirred at 100 ° C. to uniformly dissolve. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g of tetrahydrophthalic anhydride were added to the resulting reaction liquid, reacted at 110 ° C. for 4 hours, and after cooling, the solid content acid value 89 mgKOH / g, solid content 65 % Carboxyl group-containing resin was obtained. This is designated as resin solution A-1.

(Synthesis Example 2)
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device, 119.4 g of a novolac type cresol resin (manufactured by Showa Denko KK, trade name “Shonol CRG951”, OH equivalent: 119.4) Then, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the inside of the system was purged with nitrogen while stirring, and the temperature was raised. Next, 63.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group. 293.0 g of the obtained novolak-type cresol resin alkylene oxide reaction solution, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, a thermometer and an air blowing tube. The reaction vessel was charged with air at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours while stirring. As the water produced by the reaction, 12.6 g of water was distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 g of the obtained novolac acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours. A carboxyl group-containing resin having a solid acid value of 88 mgKOH / g and a solid content of 71% was obtained. This is designated as resin solution A-2.

Using the above resin solution, blended in the blend (part by mass) shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and photocured in Examples 1-6 and Comparative Examples 1-6. A functional resin composition was prepared.
In addition, when the dispersion degree of the obtained photocurable resin composition was evaluated by the particle size measurement by the grindometer made from Eriksen, it was each 15 micrometers or less.

Photopolymerization initiator B-1: 2,4,6-trimethylbenzoin diphenylphosphine oxide photopolymerization initiator B-2: bis (2,4,6-trimethylbenzoyl) phenylphosphine photopolymerization initiator B-3: bis ( η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium photoinitiator B-4: 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) -butanone-1
Polymerization inhibitor C-1: 4-methoxy 1-naphthol Kawasaki Chemical Industries Kinopower MNT
Polymerization inhibitor C-2: Phenothiazine Seiko Chemical Co., Ltd. filler D-1: Barium sulfate B-30, Sakai Chemical Industry Co., Ltd.
Filler D-2: Silica Admatech's SO-E2
Filler D-3: Talc SG-2000 made by Nippon Talc
* 1: Dipentaerystol hexaacrylate * 2: Phenol novolac epoxy resin * 3: Triglycidyl isocyanurate * 4: Melamine * 5: Pigment Blue 15: 3
* 6: Pigment Yellow 147
* 7: Dipropylene glycol monomethyl ether

(Characteristic evaluation)
Each photocurable resin composition of each of the above Examples and Comparative Examples was applied on the entire surface by screen printing on a substrate, dried for 30 minutes in a hot air circulation drying oven at 80 ° C., and then allowed to cool to room temperature. This substrate was exposed at an optimum exposure amount using an exposure apparatus mounted with a high-pressure mercury lamp (exposure machine manufactured by Oak Manufacturing Co., Ltd.), temperature: 30 ° C., spray pressure: 0.2 MPa, developer: 1% by mass. Development was performed for 60 seconds under the condition of an aqueous sodium carbonate solution to obtain a pattern. Further, this substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 160 ° C. for 60 minutes. About the obtained printed circuit board (evaluation board | substrate), the characteristic was evaluated as follows. The optimal exposure amount was determined when the exposure was performed via a step tablet (Stouffer T4105C) during exposure, and the number of step tablet remaining after development was eight.

(Resolution)
On the copper foil substrate, using a negative pattern having a via opening diameter of 60 μm as a negative mask for evaluation, an opening pattern of the photocurable resin composition is prepared, and the diameter at the bottom portion of the opening portion of the obtained evaluation substrate is set. Observation and measurement were performed with a 1000 × scanning electron microscope, and evaluation was performed under the following evaluation conditions.
A: The diameter is more than 55 μm to 60 μm or less. ○: The diameter is more than 50 μm to 55 μm or less.

(Adhesion)
A line pattern of a photocurable resin composition is prepared on a substrate having a surface roughness Ra = 700 nm using a negative pattern having a line width of 100 μm as a negative mask for evaluation, and a cross-sectional shape of a line of the obtained evaluation substrate is obtained. Observation was performed with an optical microscope, and evaluation was performed under the following evaluation conditions. A photograph showing an example of no peeling is shown in FIG. 1, and a photograph showing an example of peeling is shown in FIG. FIG. 1 and FIG. 2 are photographic views of a cross-sectional shape of a line pattern of a photocurable resin composition taken with a camera connected to an optical microscope. In the photo with peeling, it can be seen that both ends of the line are floating.
○: No peeling ×: There is peeling

(HAST resistance)
A cured coating film of a photocurable resin composition was formed on a BT substrate on which comb-type electrodes (line / space = 50 μm / 50 μm) were formed, and an evaluation substrate was prepared. This evaluation board | substrate was put into the high temperature / humidity tank of the atmosphere of 130 degreeC and humidity 85%, the voltage 12V was charged, and the in-chamber HAST test was done for 168 hours. The insulation resistance value in the tank when 168 hours passed was evaluated according to the following criteria.
○: More than 10 ⁸ Ω Δ: 10 ⁶ to 10 ⁸ Ω
×: Less than 10 ⁶ Ω

(Working environment stability)
The photocurable resin compositions of Examples 1 to 6 and Comparative Examples 1 to 6 were all coated on a copper foil substrate by screen printing, dried in a hot air circulation drying oven at 80 ° C. for 30 minutes, and then to room temperature. Allow to cool. The substrate is left in a laboratory with a yellow lamp and a room temperature of 25 ° C. for 12 hours, and then developed for 60 seconds with a temperature of 30 ° C., a spray pressure of 0.2 MPa, and a developer of 1% by mass of sodium carbonate aqueous solution. The substrate after development was evaluated according to the following criteria. The generation of the residue means that the photocuring reaction proceeds under a yellow lamp, which means that stability is applied.
○: No residue △: There is a slight residue ×: There is a residue

As shown in Table 2, all of Examples 1 to 6 were excellent in resolution and adhesion, and there was no problem in HAST resistance and work environment stability.
On the other hand, in Comparative Examples 1 to 5 lacking at least one of acylphosphine oxide photopolymerization initiator and titanocene photopolymerization initiator, resolution and adhesion are at least as compared with the respective examples. Any one characteristic was inferior. Further, Comparative Example 6 lacking a polymerization inhibitor was inferior in working environment stability as compared with each Example.

Claims (9)

(A) a carboxyl group-containing resin,
(B) an acylphosphine oxide photopolymerization initiator,
(C) a titanocene photopolymerization initiator,
(D) a photosensitive monomer, and (E) a polymerization inhibitor, wherein (A) the carboxyl group-containing resin is
(A-1) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide is reacted with an unsaturated group-containing monocarboxylic acid, and the resulting reaction product is polybasic. A carboxyl group-containing photosensitive resin obtained by reacting an acid anhydride,
(A-2) A carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or higher polyfunctional (solid) epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group present in the side chain ,
(A-3) A polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. Carboxyl group-containing photosensitive resin,
(A-4) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound. A carboxyl group-containing photosensitive resin obtained by reacting a basic acid anhydride,
(A-5) carboxyl group-containing photosensitive urethane resin by polyaddition reaction of diisocyanate and (meth) acrylate of bifunctional epoxy resin or its partial acid anhydride modified product, carboxyl group-containing dialcohol compound and diol compound,
(A-6) carboxyl group-containing non-photosensitive urethane resin by polyaddition reaction of diisocyanate, carboxyl group-containing dialcohol compound and polyol or diol compound,
(A-7) a carboxyl group-containing non-photosensitive polyester resin obtained by reacting a difunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group,
(A-8) During the synthesis of the resin (A-5) or (A-6), a compound having one hydroxyl group and one or more (meth) acryloyl groups in the molecule is added, and the terminal (meth) is added. Acrylic carboxyl group-containing photosensitive urethane resin,
(A-9) During the synthesis of the resin (A-5) or (A-6), a compound having one isocyanate group and one or more (meth) acryloyl groups in the molecule was added to the terminal (meth). Acrylic carboxyl group-containing photosensitive urethane resin,
(A-10) A carboxyl group-containing product obtained by adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule to the resins (A-1) to (A-9). Photosensitive resin,
A photocurable resin composition comprising at least one of them. The photocurable resin composition according to claim 1, wherein the (B) acylphosphine oxide photopolymerization initiator is a compound having a partial structure represented by the following general formula (I).
Wherein R ¹ and R ² are each independently a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms. , An aryl group having 6 to 20 carbon atoms which may be substituted with at least any one of a cycloalkyl group having 5 to 20 carbon atoms, an alkyl group and an alkoxy group, or at least one of an alkyl group and an alkoxy group Or an arylcarbonyl group having 7 to 20 carbon atoms which may be substituted with one kind.) The photocurable resin composition according to claim 1 or 2, wherein the (C) titanocene photopolymerization initiator is a compound represented by the following general formula (II).
Wherein R ³ and R ⁴ are each independently substituted with one or more substituents selected from a halogen atom, an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkoxyalkylcarbonyl group, an aryl group and a heterocyclic group. Represents an optionally substituted aryl group having 6 to 20 carbon atoms.) The photocurable resin composition according to any one of claims 1 to 3, wherein the (C) titanocene photopolymerization initiator is a compound represented by the following formula.
  The photocurable resin composition according to any one of claims 1 to 4, wherein the polymerization inhibitor (E) contains at least one of a naphthalene derivative, a naphthoquinone, and a naphthoquinone derivative.   The photocurable resin composition according to any one of claims 1 to 5, wherein the (A) carboxyl group-containing resin contains a carboxyl group-containing resin obtained using a phenol compound as a starting material.   A dry film obtained by applying and drying the photocurable resin composition according to any one of claims 1 to 6 on a film.   Hardened | cured material formed by hardening the photocurable resin composition as described in any one of Claims 1-6, or the dry film of Claim 7.   A printed wiring board comprising the cured product according to claim 8.