JP2010237578A - Photocurable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable resin composition that is superior in dry-to-touch property, developability, and through-hole developability, and also achieves soldering heat resistance, electroless gold plating resistance, and electrical characteristicss equal to or higher than conventional those when being cured. <P>SOLUTION: An alkali-developable photocurable resin composition contains a hydroxy group-containing resin expressed by general formula (I), a carboxyl group-containing resin, and a photopolymerization initiator. In general formula (I): R<SP>1</SP>represents a hydronen atom or a 1-20C organic group; R<SP>2</SP>represents at least one functional group selected from a group consisting of a 1-10C alkyl group, a 1-10C alkylene group, and phenylene groups; R<SP>3</SP>represents a hydrogen atom or a 1-4C alkyl group; R<SP>4</SP>represents a hydrogen atom or a 1-4C alkyl group; p represents an integer of 1-5; q represents an integer of ≥2; m represents an integer of 1-4; and n represents an integer of 1-10. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photo-curable resin composition that is used for, for example, a solder resist of a printed wiring board or a flexible printed wiring board and that can be developed with a dilute alkaline aqueous solution.

  For example, alkali developable photosensitive compositions are widely used as solder resists for printed wiring boards. The solder resist is intended to protect the circuit of the printed circuit board, and is formed on the surface layer of the circuit board on which the circuit is formed. In general, a circuit is formed on the substrate on which the circuit is formed, and many through holes are arranged.

  When a solder resist is applied to or laminated on a circuit board having such a through hole, the solder resist flows into the through hole, which makes it difficult to remove the resist. Therefore, it is conceivable to extend the development time and remove the resist flowing into the through hole. However, an increase in development time not only reduces productivity, but also causes an excessive developer attack, which not only causes undercutting in the required fine shape, but also makes it difficult to form a pattern. Yes. In particular, such problems have become more conspicuous because the printed wiring boards are becoming denser, multilayered, and through-holes are becoming smaller due to recent reductions in the size of electronic components.

  On the other hand, in the developability of a solder resist, the influence of hydrophilic groups such as carboxyl groups and / or hydroxyl groups in organic substances used in the composition is large, and the design of resins having carboxyl groups and / or hydroxyl groups is very important. is there. So far, many solder resist compositions mainly composed of carboxyl group-containing epoxy acrylate obtained by adding a polybasic acid anhydride to a reaction product of a novolak type epoxy resin and acrylic acid have been reported. .

  However, in this solder resist composition, the acid value of the carboxyl group-containing epoxy acrylate must be relatively high in order to perform development satisfactorily using a dilute alkaline aqueous solution. When such a carboxyl group-containing epoxy acrylate having a relatively high acid value is used, problems such as swelling and peeling of the cured product of the solder resist occur when performing electroless gold plating. Furthermore, by applying a solder resist composition to the substrate, drying the solvent, and leaving it for a long time, there is a problem in that an unexposed portion is not developed with a dilute alkaline aqueous solution and a development residue is generated (see, for example, Patent Document 1). ).

Japanese Patent No. 1799319 (Claims)

  The present invention has been made to solve such problems, and can obtain excellent touch drying properties, developability, and through-hole developability, and the cured product thereof is equal to or more than the conventional one. An object of the present invention is to provide a photocurable resin composition capable of obtaining solder heat resistance, electroless gold plating resistance, and electrical characteristics.

In order to achieve such an object, according to one embodiment of the present invention, the resin composition contains a hydroxyl group-containing resin represented by the general formula (I), a carboxyl group-containing resin, and a photopolymerization initiator. An alkali-developable photocurable resin composition is provided.

(In the formula, R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, which may be the same or different, and R ² is an alkyl group having 1 to 10 carbon atoms or an alkylene group having 1 to 10 carbon atoms. And at least one functional group selected from the group consisting of a phenylene group, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Represents a group, p represents an integer of 1 to 5, q represents an integer of 2 or more, m represents an integer of 1 to 4, and n represents an integer of 1 to 10).
With such a configuration, it is possible to obtain excellent dryness to touch, developability, and through-hole developability, and in the cured product, solder heat resistance, electroless gold plating resistance, electrical resistance, It becomes possible to obtain characteristics.

  In the photocurable resin composition of one embodiment of the present invention, the hydroxyl group-containing resin is a compound obtained by reacting a cyclic ether compound or a cyclic carbonate compound with a compound having two or more phenolic hydroxyl groups in one molecule. Is preferred.

  In the photocurable resin composition of one embodiment of the present invention, the softening point of the compound having two or more phenolic hydroxyl groups in one molecule is preferably room temperature or higher.

  In the photocurable resin composition of one embodiment of the present invention, it is preferable to further contain a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule.

  The photocurable resin composition of one embodiment of the present invention may further contain a urethanization catalyst. Curing of a hydroxyl group and an isocyanate group can be promoted.

  The photocurable resin composition of one embodiment of the present invention may further contain a thermosetting component. Heat resistance can be imparted.

  The photocurable resin composition of one embodiment of the present invention can further contain a colorant.

  Moreover, the hardened | cured material which apply | coated such a photocurable resin composition on a base material and photocured is provided. In such a cured product, a copper layer can be used as a substrate. Moreover, the applied photocurable resin composition can be photocured in a pattern.

  Moreover, while applying such a photocurable resin composition to a carrier film and drying it, the photocurable dry film is provided, and the hardened | cured material which affixed this on the base material is provided. In such a cured product, a copper layer can be used as a substrate. Moreover, the pasted photocurable dry film can be photocured in a pattern.

  Furthermore, the printed circuit board provided with the hardened | cured material obtained by doing in this way can be provided.

  According to the photocurable resin composition of the present invention, excellent touch drying property, developability, and through-hole developability can be obtained, and in the cured product, solder heat resistance, Electroless gold plating properties and electrical characteristics can be obtained.

The photocurable resin composition of this embodiment contains a hydroxyl group-containing resin represented by the general formula (I), a carboxyl group-containing resin, and a photopolymerization initiator.

(In the formula, R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, which may be the same or different, and R ² is an alkyl group having 1 to 10 carbon atoms or an alkylene group having 1 to 10 carbon atoms. And at least one functional group selected from the group consisting of a phenylene group, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Represents a group, p represents an integer of 1 to 5, q represents an integer of 2 or more, m represents an integer of 1 to 4, and n represents an integer of 1 to 10).
And it has the characteristics in the point which uses the photosensitive resin which has a structure shown by General formula (I) which has a hydroxyl group.

  In particular, by using a compound obtained by reacting a cyclic ether compound or a cyclic carbonate compound with a compound having two or more phenolic hydroxyl groups in one molecule as a hydroxyl group-containing resin having a structure represented by the general formula (I). Since a hydrophilic alcoholic hydroxyl group is produced, the developability with an alkaline aqueous solution is improved by containing it together with a carboxyl group-containing resin. Furthermore, in the cured product, a decrease in electroless gold plating resistance is suppressed.

  According to the study by the present inventors, the photocurable resin composition obtained by containing a hydroxyl group-containing resin having a structure represented by the general formula (I) has excellent developability and contains this compound. It was found that the developability of the through-hole was better than when not. Furthermore, it was found that with the increase in the amount of these compounds used, the elongation rate of the cured product (cured film) was improved, and an improvement in crack resistance, flexibility and punching resistance of the cured product could be expected. In particular, when a compound obtained by reacting a cyclic ether compound or a cyclic carbonate compound with a compound having two or more phenolic hydroxyl groups in one molecule is used as this compound, it is found that the dryness to touch improves. It was.

  As the hydroxyl group-containing resin having a structure represented by the general formula (I) in the present embodiment, those synthesized by a known method can be used. Among these, a compound obtained by reacting a cyclic ether compound or a cyclic carbonate compound with a compound having two or more phenolic hydroxyl groups in one molecule can be suitably used.

  Examples of the compound having two or more phenolic hydroxyl groups in one molecule include novolac type phenol resins. The novolac type phenol resin is obtained by a condensation reaction between phenols and formaldehyde, and these reactions are usually performed in the presence of an acidic catalyst. Phenols used in the synthesis of novolac type phenol resins include phenol, cresol, ethylphenol, propylphenol, butylphenol, hexylphenol, octylphenol, nonylphenol, phenylphenol, cumylphenol, bisphenol A, bisphenol F, bisylenol, etc. These may be used alone or in combination. Further, condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group, poly-p-hydroxystyrene, 1-naphthol or condensates of 2-naphthol and aldehydes (namely, naphthol type novolak resin), 1, 2 -, 1,3-, 1,4-, 1,5-, 1,6-, 2,3-, 2,6-, 2,7-dihydroxynaphthalene and aldehydes, mononaphthol and the above Condensates of dihydroxynaphthalene and aldehydes, condensates of mono or dihydroxynaphthalene and xylylene glycols, adducts of mono or dihydroxynaphthalene and diene compounds, condensates of phenols and bis (methoxymethyl) biphenyl, etc. However, it is not limited to these. Moreover, it is preferable to use these phenol resins having an average phenol nucleus number of 3 or more.

  Among the cyclic ether compound or the cyclic carbonate compound in the present embodiment, examples of the cyclic ether compound include ethylene oxide, propylene oxide, 1,2-butylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran. Examples of the cyclic carbonate compound include ethylene carbonate and / or propylene carbonate. Particularly preferred are ethylene oxide and propylene oxide.

  It is preferable that the compounding quantity of the hydroxyl-containing resin shown by general formula (I) is 1-100 mass parts with respect to 100 mass parts of carboxyl group-containing resin, for example. When the compounding quantity of hydroxyl-containing resin exceeds 100 mass parts, the heat resistance of the hardened | cured material obtained will fall. On the other hand, when the amount is less than 1 part by mass, developability is impaired. More preferably, it is 5-60 mass parts, More preferably, it is the range of 10-40 mass parts.

  The carboxyl group-containing resin in the present embodiment is used for the purpose of imparting alkali developability. As such a carboxyl group-containing resin, various known carboxyl group-containing resins having a carboxyl group in the molecule can be used. In particular, from the viewpoint of photocurability and development resistance, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferable. And the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof.

  As specific examples of such a carboxyl group-containing resin, the following compounds (any of oligomers and polymers) may be preferable.

  (1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.

  (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (3) 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 ( Photosensitive carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its modified partial anhydride, carboxyl group-containing dialcohol compound and diol compound.

  (4) During the synthesis of the resin of the above (2) or (3), a compound having one hydroxyl group and one or more (meth) acryl groups in the molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( Photosensitive carboxyl group-containing urethane resin that has been meta-acrylated.

  (5) During the synthesis of the resin of the above (2) or (3), one isocyanate group and one or more (meth) acryl groups are added in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. The photosensitive carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.

  (6) A photosensitive carboxyl group obtained by reacting a bifunctional or higher polyfunctional (solid) epoxy resin as described later with (meth) acrylic acid and adding a dibasic acid anhydride to the hydroxyl group present in the side chain. Containing resin.

  (7) 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 photosensitive carboxyl group-containing resin.

  (8) A carboxyl group-containing polyester resin obtained by reacting a bifunctional oxetane resin as described later with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.

  (9) A photosensitive carboxyl group-containing resin obtained by adding a compound having one epoxy group and one or more (meth) acryl groups in one molecule to the resins (1) to (8).

  These carboxyl group-containing resins are not limited to these, and can be used alone or in combination of two or more.

  Here, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to similar expressions hereinafter.

  Since such a carboxyl group-containing resin has a number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.

  Moreover, it is preferable that the acid value of carboxyl group-containing resin is the range of 40-200 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, if it exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line becomes thinner than necessary, or in some cases, dissolution and peeling occur with the developer without distinguishing between the exposed portion and the unexposed portion. It becomes difficult to draw a normal resist pattern. More preferably, it is the range of 45-120 mgKOH / g.

  Moreover, although the weight average molecular weight of carboxyl group-containing resin changes with resin frame | skeleton, it is preferable that it is generally 2,000-150,000. When the weight average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, the film may be reduced during development, and the 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. More preferably, it is in the range of 5,000 to 100,000.

  It is preferable that the compounding quantity of such carboxyl group-containing resin is 20-60 mass% in the whole composition. When it is less than 20% by mass, the film strength is lowered. On the other hand, when it exceeds 60 mass%, the viscosity of a composition will become high and applicability | paintability etc. will fall. More preferably, it is the range of 30-50 mass%.

As the photopolymerization initiator of this embodiment, an oxime ester photopolymerization initiator having a group represented by the general formula (II), an α-aminoacetophenone photopolymerization having a group represented by the general formula (III) One or more photopolymerization initiators selected from the group consisting of initiators and / or acylphosphine oxide photopolymerization initiators having a group represented by formula (IV) are preferred.

(In the formula, R ⁶ represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more). Or may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or benzoyl. Represents a group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R ⁷ is a phenyl group (substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom). Or an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), carbon number 5 ˜8 cycloalkyl groups, Represents an alkanoyl group or a benzoyl group prime 2-20 (carbon atoms may be substituted with 1-6 alkyl or phenyl group), R ⁸ and R ⁹ are each independently, a carbon number 1 to 12 R ¹⁰ and R ¹¹ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded, and R ¹² and R ^13. Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl group substituted with a halogen atom, an alkyl group or an alkoxy group, provided that , R ¹² and R ¹³ may represent an R—C (═O) — group (where R represents a hydrocarbon group having 1 to 20 carbon atoms).
Examples of the oxime ester photopolymerization initiator having a group represented by the general formula (II) include 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the formula (V), and the general formula (VI). And a compound represented by the general formula (VII) are preferred.

(In the formula, R ¹⁴ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or 2 carbon atoms. To 12 alkoxycarbonyl groups (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and one or more oxygen atoms in the middle of the alkyl chain) Or a phenoxycarbonyl group, and each of R ¹⁵ and R ¹⁷ may be independently substituted with a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom). Good), an alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, and have one or more oxygen atoms in the middle of the alkyl chain) Good), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R ¹⁶ Is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which is substituted with one or more hydroxyl groups). Or may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 1 carbon atoms). 6 may be substituted with 6 alkyl groups or phenyl groups).

(Wherein R ¹⁸ , R ¹⁹ and R ²⁴ each independently represents an alkyl group having 1 to 12 carbon atoms, and R ²⁰ , R ²¹ , R ²² and R ²³ each independently represents a hydrogen atom or a carbon atom. (Expression 1 represents an alkyl group of 1 to 6, M represents O, S or NH, and x and y each independently represents an integer of 0 to 5).
Among these oxime ester photopolymerization initiators, 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by general formula (V) and a compound represented by general formula (VI) are more preferable. Examples of commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Specialty Chemicals, N-1919 manufactured by ADEKA, and the like. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.

  As the α-aminoacetophenone photopolymerization initiator having a group represented by the general formula (III), 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 Ciba Specialty Chemicals.

  Acylphosphine oxide photopolymerization initiators having a group represented by the general formula (IV) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. And bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.

  It is preferable that the compounding quantity of such a photoinitiator is 0.01-30 mass parts with respect to 100 mass parts of carboxyl group-containing resin. When the blending amount of the photopolymerization initiator is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off or the coating properties such as chemical resistance are deteriorated. On the other hand, when it exceeds 30 parts by mass, light absorption on the surface of the solder resist coating film of the photopolymerization initiator becomes intense, and the deep curability tends to decrease. More preferably, it is the range of 0.5-15 mass parts.

  In the case of the oxime ester photopolymerization initiator having a group represented by the general formula (II), the blending amount is 0.01 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. Is preferred. More preferably, it is the range of 0.01-5 mass parts.

  In addition, as a photopolymerization initiator, a photoinitiator assistant and a sensitizer that can be suitably used for the photocurable resin composition of the present embodiment, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, Examples include benzophenone compounds, xanthone compounds, and tertiary amine 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, and 1,1-dichloroacetophenone.

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

  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, for example, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, 4-benzoyl-4′-propyldiphenyl. Sulfide.

  Specific examples of the tertiary amine compound include, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylamino. Dialkylamino benzophenone such as benzophenone (EAB manufactured by Hodogaya Chemical Co.), and dialkylamino groups such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin) Containing coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylaminobenzoic acid ( -Butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (manufactured by Van Dyk) Esolol 507), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).

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

  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 carboxyl group-containing resin. This is because if the amount of the thioxanthone compound is too large, the thick film curability is lowered and the cost of the product is increased. More preferably, the ratio 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 and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has a maximum absorption wavelength in the ultraviolet region, so that it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition. A colored solder resist film reflecting the color 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 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 dry solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease. More preferably, it is a ratio of 0.1 to 10 parts by mass.

  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 in the range of 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  In order to improve sensitivity, the photocurable resin composition of the present embodiment can contain known N phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole, and the like as chain transfer agents. . Specific examples of chain transfer agents include, for example, chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol Chain transfer agents having a hydroxyl group, such as 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2, 2 -(Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclo Ntanchioru, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol like.

  Further, examples of the heterocyclic compound having a mercapto group acting as a chain transfer agent 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-va Lolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto- Examples include 5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, and 2-mercapto-6-hexanolactam.

  In particular, as a heterocyclic compound having a mercapto group, which is a chain transfer agent that does not impair the developability of the photocurable resin composition, mercaptobenzothiazole, 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. These chain transfer agents can be used alone or in combination of two or more.

  In order to improve curability and toughness of the resulting cured film, a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is added to the photocurable resin composition of the present embodiment. be able to.

  As such a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule, a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound, or 2 in one molecule. Examples include compounds having one or more blocked isocyanate groups, that is, blocked isocyanate compounds.

  As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include 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, adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.

  The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by a reaction with a blocking agent and temporarily deactivated. And when it heats to predetermined temperature, the blocking agent dissociates and an isocyanate group produces | generates.

  As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As this isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include 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.

  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, lactic acid And alcohol-based blocking agents such as ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methylethyl 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 It is.

  A commercially available block isocyanate compound can be used, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS- 2117, Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nippon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B -846, B-870, B-874, B-882 (trade name, made by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (trade name, made by Asahi Kasei Chemicals Corp.) and the like. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

  These compounds having two or more isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.

  The compounding amount of the compound having two or more 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 carboxyl group-containing resin. When the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained. On the other hand, when it exceeds 100 mass parts, storage stability falls. More preferably, it is the ratio of 2-70 mass parts.

  A urethanization catalyst can be added to the photocurable resin composition of the present embodiment in order to promote curing of hydroxyl groups and isocyanate groups. As the urethanization catalyst, it is possible to use one or more urethanization catalysts selected from the group consisting of tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds, and / or amine salts. preferable.

  Examples of the tin-based catalyst include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.

  The metal chloride is a metal chloride made of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include cobalt chloride, ferrous nickel chloride, and ferric chloride.

  The metal acetylacetonate salt is a metal acetylacetonate salt made of Cr, Mn, Co, Ni, Fe, Cu or Al, for example, cobalt acetylacetonate, nickel acetylacetonate, iron acetylacetonate, etc. Can be mentioned.

  The metal sulfate is a metal sulfate composed of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include copper sulfate.

  Examples of the amine compound include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N ′-( 2-hydroxyethyl) -N, N, N′-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethyl-N ′ -(2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) -N, N ', N ", N" -tetramethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N', N ", N" -tetramethyldiethylenetriamine, N, N, N'-trimethyl-N '-(2-hydroxyethyl) propanediamine, N-methyl-N'-(2-hydroxyethyl) piperazine, bis (N, N-dimethylaminopropyl) amine, bis (N, N-dimethylaminopropyl) isopropanolamine 2-aminoquinuclidine, 3-aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidol, 3-quinuclidinol, 4-quinuclidinol, 1- (2′-hydroxypropyl) imidazole, 1- ( 2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imidazole 1- (2′-hydroxyethyl) -2-methylimidazole, 1- (2′-hydroxypropyl) -2-methylimidazole, 1- (3′-aminopropyl) imidazole, 1- (3′-aminopropyl) ) -2-methylimidazole, 1- (3′-hydroxypropyl) imidazole, 1- (3′-hydroxypropyl) -2-methylimidazole, N, N-dimethylaminopropyl-N ′-(2-hydroxyethyl) Amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxypropyl) amine, N, N-dimethylaminoethyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminoethyl-N ′, N ′ -Bis (2-hydroxypropyl) amine, melamine or / and benzoguanamine etc. are mentioned.

  Examples of the amine salt include an organic acid salt amine salt of DBU (1,8-diaza-bicyclo [5,4,0] undecene-7).

  The compounding amount of the urethanization catalyst is sufficient in an ordinary quantitative ratio, and for example, it is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. More preferably, it is 0.5-10.0 mass parts.

  A thermosetting component can be added to the photocurable resin composition of the present embodiment in order to impart heat resistance. For example, known thermosetting resins such as melamine resins, melamine derivatives, benzoguanamine resins, amine resins such as benzoguanamine derivatives, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, and episulfide resins can be used. Among these, a thermosetting component having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule is particularly preferable.

  Such a thermosetting component having two or more cyclic (thio) ether groups in the molecule is either one of the three-, four- or five-membered cyclic ether groups in the molecule, or the cyclic thioether group, or two of them. A compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having at least two oxetanyl groups in the molecule, that is, a polyfunctional compound. Examples include oxetane compounds, compounds having two or more thioether groups in the molecule, that is, episulfide resins.

  Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, and Epoto YD manufactured by Tohto Kasei Co., Ltd. -011, YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Specialty Chemicals' Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Industries Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Corporation A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. 664 etc. (all trade names) bisphenol A type epoxy resin; jERYL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd. D. Chemicals manufactured by Dow Chemical Company. E. R. 542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R. 714 (both trade names) brominated epoxy resin; jER152, jER154 manufactured by Japan Epoxy Resin, D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 from Toto Kasei Co., Ltd., Araldide ECN1235 from Ciba Specialty Chemicals, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., Sumi-epoxy ESCN-195X, ESCN- manufactured by Sumitomo Chemical 220, manufactured by Asahi Kasei Corporation. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by Dainippon Ink and Chemicals, jER807 manufactured by Japan Epoxy Resin, Epototo YDF-170 manufactured by Toto Kasei Co., Ltd., YDF- 175, YDF-2004, Araldide XPY306 manufactured by Ciba Specialty Chemicals, etc. (both trade names); Epototo ST-2004, ST-2007, ST-3000 (trade names, manufactured by Toto Kasei) Hydrogenated bisphenol A type epoxy resin such as JER604 manufactured by Japan Epoxy Resin Co., Ltd., Epotot YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd. -120 etc. (both Product name) Glycidylamine type epoxy resin; Ardandide type epoxy resin such as araldide CY-350 (trade name) made by Ciba Specialty Chemicals; Celoxide 2021 made by Daicel Chemical Industries, Araldide made by Ciba Specialty Chemicals CY175, CY179, etc. (both trade names); YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc. Xylenol type or biphenol type epoxy resin or a mixture thereof; bisphenol S type such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin; jERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals (all trade names) Tetraphenylolethane type epoxy Fatty; heterocyclic epoxy resins such as Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; Toto Kasei Co., Ltd. Tetraglycidylxylenoylethane resins such as ZX-1063 manufactured by Nippon Steel; ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. Naphthalene group-containing epoxy such as HP-4032, EXA-4750, and EXA-4700 manufactured by Dainippon Ink & Chemicals, Inc. Resin; Epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink &Chemicals; Glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by Nippon Oil &Fats; Cyclohexylmaleimide and glycidyl methacrylate Relate copolymerized epoxy resins; epoxy-modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industries), CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd.), and the like. However, it is not limited to these. These epoxy resins can be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.

  Polyfunctional oxetane compounds 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-oxetanyl) In addition to polyfunctional oxetanes such as 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 bisphenol , Calixarenes, calix resorcin arenes, or the like ethers of a 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 two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resin Co., Ltd. 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 two or more cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents relative to 1 equivalent of carboxyl group of the carboxyl group-containing resin. . When the amount of the thermosetting component having two or more cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, and heat resistance, alkali resistance, electrical insulation, etc. Decreases. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dried coating film, thereby reducing the strength of the coating film. More preferably, it is 0.8-2.0 equivalent.

  Furthermore, amine resins, such as a melamine derivative and a benzoguanamine derivative, are mentioned as a thermosetting component. Examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the 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 (above, manufactured by Mitsui Cyanamid Co., Ltd.), 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, (manufactured by Sanwa Chemical Co., Ltd.) and the like. These thermosetting components can be used alone or in combination of two or more.

  When using a thermosetting component having two or more cyclic (thio) ether groups in the molecule, 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, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can 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 / isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used. Furthermore, it is preferable to use these compounds that also function as adhesion promoters in combination with a thermosetting catalyst.

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

  In the photocurable resin composition of the present embodiment, an adhesion promoter can be further used to improve the adhesion between layers or the adhesion between the photosensitive resin layer and the substrate. Specific examples include, for example, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2- Thion, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent, etc. is there.

  The photocurable resin composition of the present embodiment can further contain a colorant. As the colorant, known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and pigments may be used. 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 the red colorant include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Can be mentioned.

  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 classified as Pigment, specifically, the following color index (CI; The Society of Dyers) And Colorists (issued by The Society of Dyers and Colorists) are numbered: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60, and the like.

  The dye system includes 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 these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

(Green colorant)
Similarly, there are phthalocyanine, anthraquinone, and perylene types as green colorants. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. are used. be able to. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds 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, for the purpose of adjusting the color tone, a colorant such as purple, orange, brown, or black may be added.

  Specifically, 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 , Mention may be made of the C.I. Pigment Black 7 and the like.

  The blending ratio of such a colorant is not particularly limited, but is preferably 0 to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. More preferably, it is 0.1-5 mass parts.

  Furthermore, in the photocurable resin composition of the present embodiment, in order to help insolubilize or insolubilize the ethylenically unsaturated group-containing carboxyl group-containing resin in an alkaline aqueous solution by photocuring by irradiation with active energy rays, A compound having two or more ethylenically unsaturated groups in the molecule can be used.

  Examples of such compounds include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, and the like. Polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts or propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycy Ethers, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates.

Further, 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. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. With such an epoxy acrylate resin, photocurability can be improved without deteriorating the touch drying property. The compounding amount of a compound having two or more ethylenically unsaturated groups in such a molecule is It is preferable that it is 5-100 mass parts with respect to 100 mass parts of carboxyl group-containing resin. When the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays. On the other hand, when it exceeds 100 mass parts, the solubility with respect to alkaline aqueous solution falls, and a coating film becomes weak. More preferably, it is 1-70 mass parts.

  The photocurable resin composition of the present embodiment can be blended with a filler as necessary in order to increase the physical strength of the coating film. As such a filler, known inorganic or organic fillers can be used, but barium sulfate, spherical silica and talc are particularly preferably used. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers.

  The blending amount of such filler is preferably 75% by weight or less of the total amount of the composition. When the blending amount of the filler exceeds 75% by weight of the total amount of the composition, the viscosity of the insulating composition becomes high, the coating and moldability are lowered, and the cured product becomes brittle. More preferably, the ratio is 0.1 to 60% by weight.

  Furthermore, the photocurable resin composition of the present embodiment may use an organic solvent for the synthesis of a carboxyl group-containing resin, the preparation of the composition, or the viscosity adjustment for application to a substrate or a carrier film. it can.

  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, petroleum naphtha, hydrogenated petroleum naphtha, petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

  In many polymer materials, once oxidation starts, oxidative degradation occurs in a chained manner, resulting in a decrease in the function of the polymer material.Therefore, the photocurable resin composition of the present embodiment prevents oxidation. (1) Radical scavengers that invalidate the generated radicals and / or (2) Peroxide decomposers that decompose the generated peroxides into harmless substances and prevent the generation of new radicals. It is preferable to add an antioxidant such as

  Specific examples of the antioxidant that acts as a radical scavenger include hydroquinone, 4-tert-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methylene-bis- (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5 Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′di-t-butyl-4-hydroxy Benzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione and other phenolic compounds, quinone-based compounds such as metaquinone and benzoquinone, bis (2,2,6,6-tetra And amine compounds such as methyl-4-piperidyl) -sebacate and phenothiazine.

  Commercially available products include, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (and above, ASAHI). Product name: IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, Ciba Specialty Chemicals) It is done.

  Specific examples of the antioxidant that acts as a peroxide decomposing agent include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3 ′. -Sulfur compounds such as thiodipropionate.

  Commercially available products include, for example, ADK STAB TPP (trade name, manufactured by Asahi Denka Co., Ltd.), Mark AO-412S (trade name, manufactured by Adeka Argus Chemical Co., Ltd.), and Sumilizer TPS (trade name, manufactured by Sumitomo Chemical Co., Ltd.) .

  Such antioxidant can be used individually by 1 type or in combination of 2 or more types.

  Since the polymer material absorbs light and thereby decomposes and deteriorates, the photocurable resin composition of the present embodiment contains an ultraviolet absorber in addition to the antioxidant for stabilization against ultraviolet rays. Can be used.

  Examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like. Specific examples of benzophenone derivatives include 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and 2,2′-dihydroxy-4-methoxybenzophenone. And 2,4-dihydroxybenzophenone and the like; specific examples of benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, p-tert-butylphenyl salicylate, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc .; specific examples of benzotriazole derivatives include 2- (2′- Hydroxy-5'-t-butylphenyl) Zotriazole, 2- (2′-hydroxy-5′-methylphenyl) enzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy -3 ', 5'-di-tert-amylphenyl) benzotriazole; Examples of specific triazine derivatives include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.

  Examples of commercially available products include TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (and more Chemicals, product name) and the like.

  Such ultraviolet absorbers can be used singly or in combination of two or more, and by using in combination with an antioxidant, a cured product obtained from the photocurable resin composition of the present embodiment ( Stabilization of the molded product) can be achieved.

  The photo-curable resin composition of the present embodiment further includes, as necessary, a known thermal polymerization inhibitor, a known thickener such as fine powder silica, organic bentonite, and montmorillonite, silicone-based, fluorine-based, polymer-based, etc. Known additives such as an antifoaming agent and / or a leveling agent, silane coupling agents such as imidazole, thiazole, and triazole, antioxidants, rust inhibitors, and the like can be blended.

  The thermal polymerization inhibitor is used to prevent thermal polymerization or temporal polymerization of the polymerizable compound. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

  The photocurable resin composition of the present embodiment configured as described above is used as follows. For example, the photocurable resin composition is adjusted to a viscosity suitable for the coating method using an organic solvent, and on the substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain coating method. It is applied by the method such as. A tack-free coating film is formed by volatilizing and drying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C.

  The exposed part is cured by selectively irradiating the coating film formed in this manner with an active energy ray by a contact method (or non-contact method). Then, the pattern is formed by developing with a dilute alkaline aqueous solution (for example, 0.3 to 3 wt% sodium carbonate aqueous solution) to remove the unexposed portion.

  Further, for example, by thermosetting by heating to a temperature of about 140 to 180 ° C., thermosetting having a carboxyl group of the carboxyl group-containing resin and two or more cyclic ether groups and / or cyclic thioether groups in the molecule. The components react to form a cured product (cured coating film) excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.

  Here, as a base material, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth, in addition to a printed wiring board and a flexible printed wiring board that are previously formed with a copper layer or the like. / Non-woven cloth-epoxy resin, glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminate of all grades (FR-4 etc.) using composite materials such as fluororesin, polyethylene, PPO, cyanate ester, etc. A plate, a polyimide film, a PET film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.

  For volatile drying, use a hot air circulating drying furnace, IR furnace, hot plate, convection oven, etc. equipped with a heat source of the air heating system by steam, and support from the nozzle with hot air in the dryer in countercurrent contact A method of spraying on the body can be used.

  The active energy ray irradiation is performed by selectively exposing with an active energy ray through a photomask or drawing a pattern directly using a laser direct exposure machine. As drawing equipment, exposure equipment equipped with a metal halide lamp, exposure equipment equipped with a (super) high-pressure mercury lamp, exposure equipment equipped with a mercury short arc lamp, or drawing using an ultraviolet lamp such as a (super) high-pressure mercury lamp An apparatus or 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 be used.

As the active energy ray, 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. Further, the exposure amount varies depending the thickness or the like, typically 5 to 200 mJ / cm ^2, preferably from 5 to 100 mJ / cm ^2, more preferably be in the range of 5~50mJ / cm ^2.

  As the direct drawing apparatus, for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and there is no particular limitation as long as the apparatus emits laser light having a maximum wavelength of 350 to 410 nm.

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

  Moreover, a photocurable resin composition can also be used as a dry film. The dry film has a structure in which a carrier film, an insulating resin layer (solder resist layer), and a peelable cover film used as necessary are laminated in this order. Such a dry film is formed by applying and drying a photocurable resin composition on a carrier film to form an insulating resin layer (solder resist layer), and then laminating a cover film or insulating the cover film in the same manner. After forming a resin layer (solder resist layer), it can obtain by laminating | stacking these laminated bodies on a carrier film.

  As the carrier film, a thermoplastic film such as polyethylene terephthalate or polyester film having a thickness of 2 to 150 μm is used.

  For the insulating resin layer (solder resist layer), the photocurable resin composition is uniformly applied to a carrier film or a cover film with a thickness of 10 to 150 μm using a blade coater, lip coater, comma coater, film coater, etc., and dried. Formed.

  As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but a cover film having a smaller adhesive force than the solder resist layer is preferable.

  Using such a dry film, a protective film (permanent protective film) can be produced on a printed wiring board. First, the cover film is peeled off, and an insulating resin layer (solder resist layer) and a substrate on which a circuit is formed, for example, are overlapped. And these are bonded together using a laminator etc., and the insulating resin layer (solder resist layer) is formed on the base material by which the circuit was formed. The formed insulating resin layer (solder resist layer) is exposed, developed, and heat-cured in the same manner as the coating film to form a cured product (cured coating film) that becomes a protective film (permanent protective film). At this time, the carrier film may be peeled off either before exposure or after exposure.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, it cannot be overemphasized that this invention is not limited to these Examples. In the following description, “parts” and “%” are based on mass unless otherwise specified.

(Synthesis Example 1)
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device, 104 parts of a novolac type phenol resin (BRG-558, hydroxyl group equivalent 104) manufactured by Showa Polymer Co., Ltd., 50% aqueous sodium hydroxide solution 2 .6 parts and 100 parts of toluene / methyl isobutyl ketone (mass ratio = 2/1) were charged, the inside of the system was purged with nitrogen while stirring, and then heated to 150 ° C. and propylene oxide 60 at 8 kg / cm ^2. Part was gradually introduced to react. The reaction was continued for about 4 hours until the gauge pressure reached 0.0 kg / cm ^2, and then cooled to room temperature. To this reaction solution, 3.3 parts of 36% aqueous hydrochloric acid was added and mixed to neutralize sodium hydroxide. This neutralized reaction product was diluted with toluene, washed with water three times, and desolvated with an evaporator, so that the hydroxyl group equivalent was 164 g / eq. Thus, an alkylene oxide adduct of a novolac type phenol resin was obtained. This was an average of 1 mole of alkylene oxide added per equivalent of hydroxyl group.

  Furthermore, toluene was distilled off from the reaction solution with an evaporator, and carbitol acetate was added to obtain a novolak PO addition compound having a nonvolatile content of 70%. This is referred to as A-1 varnish.

(Synthesis Example 2)
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device, 104 parts of a novolac type phenol resin (BRG-558, hydroxyl group equivalent 104) manufactured by Showa Polymer Co., Ltd., 50% aqueous sodium hydroxide solution 2 .6 parts and 100 parts of toluene / methyl isobutyl ketone (mass ratio = 2/1) were charged, the inside of the system was purged with nitrogen while stirring, and then heated to 150 ° C. and propylene oxide 120 at 8 kg / cm ^2. Part was gradually introduced to react. The reaction was continued for about 4 hours until the gauge pressure reached 0.0 kg / cm ^2, and then cooled to room temperature. To this reaction solution, 3.3 parts of 36% aqueous hydrochloric acid was added and mixed to neutralize sodium hydroxide. The neutralized reaction product was diluted with toluene, washed with water three times, and desolvated with an evaporator to give a hydroxyl group equivalent of 224 g / eq. Thus, an alkylene oxide adduct of a novolac type phenol resin was obtained. This was an average of 2 moles of alkylene oxide added per equivalent of hydroxyl group.

  Furthermore, toluene was distilled off from the reaction solution with an evaporator, and carbitol acetate was added to obtain a novolak PO addition compound having a nonvolatile content of 70%. This is referred to as A-2 varnish.

(Synthesis Example 3)
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device, 219 parts of 4,4′-biphenyldiyldimethylene-phenol resin (hydroxyl equivalent 219), 2.6 parts of 50% aqueous sodium hydroxide solution , 100 parts of toluene / methyl isobutyl ketone (mass ratio = 2/1) was charged, the system was purged with nitrogen while stirring, and then the temperature was increased by heating, and 60 parts of propylene oxide was gradually added at 150 ° C. and 8 kg / cm ^2. And reacted. The reaction was continued for about 4 hours until the gauge pressure reached 0.0 kg / cm ^2, and then cooled to room temperature. To this reaction solution, 3.3 parts of 36% aqueous hydrochloric acid was added and mixed to neutralize sodium hydroxide. The neutralized reaction product was diluted with toluene, washed with water three times, and desolvated with an evaporator to give a hydroxyl group equivalent of 279 g / eq. Of 4,4′-biphenyldiyldimethylene-phenol resin was obtained. This was an average of 1 mole of alkylene oxide added per equivalent of hydroxyl group.

  Further, toluene was distilled off from the reaction solution with an evaporator, and carbitol acetate was added to obtain a biphenyl skeleton-containing novolak PO addition compound having a nonvolatile content of 70%. This is referred to as A-3 varnish.

(Synthesis Example 4)
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device, 121 parts of 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol (hydroxyl equivalent 121), 50% water 2.6 parts of an aqueous sodium oxide solution and 100 parts of toluene / methyl isobutyl ketone (mass ratio = 2/1) were charged, and the system was purged with nitrogen while stirring, then heated to 150 ° C. and 8 kg / cm ^2. Then, 60 parts of propylene oxide was gradually introduced and reacted. The reaction was continued for about 4 hours until the gauge pressure reached 0.0 kg / cm ^2, and then cooled to room temperature. To this reaction solution, 3.3 parts of 36% aqueous hydrochloric acid was added and mixed to neutralize sodium hydroxide. The neutralized reaction product was diluted with toluene, washed with water three times, and desolvated with an evaporator to give a hydroxyl group equivalent of 181 g / eq. Thus, an alkylene oxide adduct of a novolac type phenol resin was obtained. This was an average of 1 mole of alkylene oxide added per equivalent of hydroxyl group.

  Furthermore, toluene was distilled off from the reaction solution with an evaporator, and carbitol acetate was added to obtain a biphenyl-type PO addition compound having a nonvolatile content of 70%. This is referred to as A-4 varnish.

(Synthesis Example 5)
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device, 104 parts of a novolac type phenol resin (BRG-558, hydroxyl group equivalent 104) manufactured by Showa Polymer Co., Ltd., 50% aqueous sodium hydroxide solution 2 .6 parts, 100 parts of toluene / methyl isobutyl ketone (mass ratio = 2/1) were charged, and the system was purged with nitrogen while stirring, then heated to 150 ° C. and 50 parts of ethylene oxide at 8 kg / cm ^2. Was gradually introduced and allowed to react. The reaction was continued for about 4 hours until the gauge pressure reached 0.0 kg / cm ^2, and then cooled to room temperature. To this reaction solution, 3.3 parts of 36% aqueous hydrochloric acid was added and mixed to neutralize sodium hydroxide. The neutralized reaction product was diluted with toluene, washed with water three times, and the solvent was removed with an evaporator to obtain a hydroxyl group equivalent of 154 g / eq. Thus, an alkylene oxide adduct of a novolac type phenol resin was obtained. This was an average of 1 mole of alkylene oxide added per equivalent of hydroxyl group.

  Furthermore, toluene was distilled off from the reaction solution with an evaporator, and carbitol acetate was added to obtain a novolak EO addition compound having a nonvolatile content of 70%. This is called A-5 varnish.

(Comparative Synthesis Example 1)
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device, 94 parts of a monofunctional phenol compound (hydroxyl equivalent 94), 2.6 parts of 50% aqueous sodium hydroxide, toluene / methyl isobutyl ketone (mass) (Ratio = 2/1) 100 parts were charged, and the system was purged with nitrogen while stirring. Next, the temperature was raised by heating, and 50 parts of ethylene oxide was gradually introduced at 150 ° C. and 8 kg / cm ² to react. Was continued for about 4 hours until the gauge pressure 0.0 kg / cm ^2, then cooled to room temperature. To this reaction solution, 3.3 parts of 36% aqueous hydrochloric acid was added and mixed to neutralize sodium hydroxide. The neutralized reaction product was diluted with toluene, washed with water three times, and the solvent was removed with an evaporator, so that the hydroxyl group equivalent was 138 g / eq. Thus, an alkylene oxide adduct of a phenol compound was obtained. This was an average of 1 mole of alkylene oxide added per equivalent of hydroxyl group.

  Furthermore, toluene was distilled off from the reaction solution with an evaporator, and carbitol acetate was added to obtain an EO addition compound having a nonvolatile content of 70%. This is referred to as A-6 varnish.

(Carboxyl group-containing resin (B-1) synthesis example)
Orthocresol novolak type epoxy resin (Dainippon Ink Chemical Co., Ltd., EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 g, diethylene glycol monoethyl ether acetate 600 g, acrylic acid 360 g, And 1.5 g of hydroquinone was added, and the mixture was heated and stirred at 100 ° C. to dissolve uniformly. 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 % Resin solution was obtained. Hereinafter, this carboxyl group-containing resin solution is referred to as B-1 varnish.

(Synthesis example of carboxyl group-containing resin (B-2))
A novolac-type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name “Shonol CRG951”, OH equivalent: 119.4) 119. 4 g, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. 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 resulting 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 photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained. Hereinafter, this reaction solution is referred to as B-2 varnish (Examples 1 to 11 and Comparative Examples 1 to 5).
Using the thus prepared A-1 to A-6 varnishes, B-1 and B-2 varnishes, the various components shown in Table 1 were blended in the proportions (parts by mass) shown in Table 1. And after premixing with the stirrer, it knead | mixed with the 3 roll mill and prepared the photocurable resin composition for soldering resists. Here, it was 15 micrometers or less when the dispersion degree of the obtained photocurable resin composition was evaluated by the particle size measurement by the grindometer by an Erichsen company.

^{* 1} : Diethylene glycol
^{* 2} : Novolac type phenolic resin (BRG-558: Showa High Polymer Co., Ltd.)
^{* 3} : ZFR-1124 (Nippon Kayaku Co., Ltd.)
^{* 4} : 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907: Ciba Specialty Chemicals)
^{* 5:} ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- carbazol-3-yl] 1,1-(O-acetyl oxime) (OXE-02: Ciba Specialty Chemicals (Made by company)
^{* 6} : Block isocyanate (Asahi Kasei Chemicals)
^{* 7} : Phenol novolac type epoxy resin (DEN438: manufactured by Dow Chemical Company)
^{* 8} : Bixylenol type epoxy resin (YX-4000: manufactured by Japan Epoxy Resin Co., Ltd.)
^{* 9} : CIPigment Blue 15: 3
^{* 10} : CIPigment Yellow 147
^{* 11} : Antioxidant (Ciba Specialty Chemicals)
^{* 12} : B-30 (manufactured by Sakai Chemical Co., Ltd.)
^{* 13} : Dipropylene glycol monomethyl ether
^{* 14} : Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)
^{* 15:} methylated melamine resin (Co. Sanwa Chemical)

(Evaluation of photocurable resin composition and coating film)
<Optimal exposure>
The substrate on which the circuit pattern of the copper layer with a film thickness of 35 μm was formed was buffed, washed with water and dried, and then the photocurable resin compositions of Examples and Comparative Examples were applied to the entire surface by a screen printing method at 80 ° C. For 60 minutes in a hot air circulation drying oven. After drying, exposure is performed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and development (30 ° C., 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution) is performed at 60. When the measurement was performed in seconds, the optimal exposure amount was obtained when the remaining step tablet pattern was 7 steps.

<Developability>
The photocurable resin compositions of Examples and Comparative Examples were applied to a solid copper substrate by a screen printing method so as to have a thickness of about 25 μm, and dried for 30 minutes in an 80 ° C. hot air circulation drying oven. After drying, development was performed with a 1% by mass aqueous sodium carbonate solution, and the time until the dried coating film was removed was measured with a stopwatch.

<Developability of through hole>
A 1.0 mmt copper-clad laminate was drilled with a φ200 μm drill, and through-hole plating was performed by a conventional method to produce a substrate on which 400 through-holes having an actual measurement value of about φ150 μm were formed. The photocurable resin compositions of Examples and Comparative Examples were printed twice on the substrate by a screen printing method, and the holes were filled by filling the photocurable resin composition. Furthermore, it was dried for 30 minutes in a hot air circulating drying oven at 80 ° C. and cooled to room temperature. Thereafter, development was performed for 120 seconds under the condition of a spray pressure of 0.2 MPa using a 1 mass% sodium carbonate aqueous solution at 30 ° C., and evaluation was performed according to the following criteria.
◎: 100% through hole can be developed by developing once or twice ○: 100% through hole can be developed by developing 3 to 5 times △: By developing 3 to 5 times 50 to 99% through hole developable ×: Through hole developability rate of 50% or less even after 5 developments

<Finger dryness>
The photocurable resin compositions of Examples and Comparative Examples were each coated on the patterned copper foil substrate by screen printing, dried in a hot air circulation drying oven at 80 ° C. for 30 minutes, and allowed to cool to room temperature. . A PET film was pressed against this substrate, and then the sticking state of the film when the negative film was peeled off was evaluated.
◎: When the film is peeled off, there is no resistance and no mark is left on the coating film. ○: When the film is peeled off, there is no resistance at all, but the coating film has a slight mark. △: Slightly when the film is peeled off. There is resistance, and there is a trace on the coating film. X: When the film is peeled off, there is resistance and the coating film has a clear trace.

<Resolution>
A circuit pattern substrate having a line / space of 300/300 μm and a copper thickness of 35 μm was polished with buffalo, washed with water and dried, and then the photocurable resin compositions of Examples and Comparative Examples were applied by a screen printing method at 80 ° C. It was dried for 30 minutes in a hot air circulation drying oven. After drying, exposure was performed using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp). As the exposure pattern, a glass dry plate for drawing a 20/30/40/50/60/70/80/90/100 μm line in the space portion was used. The active energy ray was irradiated so that the exposure amount became the optimal exposure amount of the photocurable resin composition. After the exposure, development was performed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. to draw a pattern, and a cured coating film was obtained by heat curing at 150 ° C. for 60 minutes.

  The minimum remaining line of the cured coating film of the obtained photocurable resin composition for solder resist was measured using an optical microscope adjusted to 200 times.

<Tensile modulus, tensile strength (tensile breaking strength), elongation (tensile breaking elongation)>
The composition of each composition example and comparative composition example was applied to a PTFE (polytetrafluoroethylene) plate which had been washed and dried in advance by a screen printing method, and dried at 80 ° C. for 30 minutes in a hot air circulation drying oven. This was cooled to room temperature, exposed at an appropriate exposure amount, and developed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. for 60 seconds under a spray pressure of 2 kg / cm ² . 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 at 150 ° C. for 60 minutes in a hot air circulation drying furnace. After cooling this to room temperature, the cured coating film was peeled off from the PTFE plate to obtain an evaluation sample.

  The tensile elasticity modulus, tensile strength (tensile fracture strength), and elongation rate (tensile fracture elongation) of the obtained evaluation sample were measured with a tension-compression tester (manufactured by Shimadzu Corporation).

<Flexibility>
The composition of each Example and Comparative Example was applied by screen printing to a Kapton material (thickness 25 μm) that had been washed and dried in advance, and dried at 80 ° C. for 30 minutes in a hot-air circulating drying oven. After cooling this to room temperature, it is exposed with an appropriate exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. is applied under a spray pressure of 2 kg / cm ^2. Development was performed for 2 seconds. 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 150 ° C. for 60 minutes to obtain an evaluation sample for a folding resistance test and a flexibility test. .

A method in which one side of a film-shaped test piece prepared by processing the obtained cured film into a width of 10 mm and a length of 90 mm is placed on an electronic balance and the other side is bent until the distance between the films reaches 3 mm. The maximum load applied to the electronic balance was evaluated as the repulsive force according to the following criteria.
○: Less than 10 g Δ: Less than 10-30 g ×: 30 g or more

(Characteristic evaluation of cured film)
The photocurable resin composition of each example and comparative example was applied on the entire surface of the patterned copper foil substrate so that the film thickness after drying by screen printing was 20 μm, and dried at 80 ° C. for 30 minutes. Allow to cool to room temperature. The substrate is exposed to a solder resist pattern at an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. is applied for 60 seconds under a spray pressure of 2 kg / cm ^2. Development was performed to obtain a resist pattern. 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 150 ° C. for 60 minutes. The characteristic was evaluated as follows with respect to the obtained printed circuit board (evaluation board).

<Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.
A: No peeling is observed even after 10 seconds of immersion for 6 times or more. ○: No peeling is observed even after 10 seconds of immersion for 3 times or more. The resist layer swells and peels off within 3 seconds per second.

<Electroless gold plating resistance>
Using commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 0.5 μm and gold 0.03 μm, and the tape peeling causes the presence or absence of resist layer peeling or plating penetration. After evaluating the presence or absence, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
◎: No soaking or peeling is observed ○: Slight soaking is confirmed after plating, but does not peel after tape peeling △: Slight soaking is seen after plating, peeling is also seen after tape peeling ×: After plating There is peeling

<Electrical characteristics>
An evaluation board was produced in the same manner using a comb-type electrode pattern of line / space = 50/50 μm instead of the copper foil board. A bias voltage of DC 10 V was applied to the comb-shaped electrode, and 130 ° C., 85% R.D. H. The insulation resistance value after 100 hours was measured in the tank. The measurement voltage was DC 10V.

<Alkali resistance>
The evaluation substrate was immersed in a 10 wt% NaOH aqueous solution at 50 ° C. for 30 minutes, and soaking and dissolution of the coating film were confirmed. Further, peeling by tape beer was confirmed. The judgment criteria are as follows.
○: No soaking, melting or peeling Δ: Some soaking, melting or peeling is confirmed ×: Soaking, melting or peeling is largely confirmed

(Dry film evaluation)
After the photocurable resin compositions of Example 4 and Comparative Example 4 were appropriately diluted with methyl ethyl ketone, respectively, using an applicator, a PET film (FB-50 manufactured by Toray Industries, Inc.) so that the film thickness after drying was 20 μm. : 16 μm) and dried at 80 ° C. for 30 minutes to obtain a dry film.

<Board fabrication>
After buffing the circuit-formed substrate, the obtained dry film was pressurized with a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho) at a pressure of 0.8 MPa, 70 ° C. for 1 minute, and a vacuum of 133. Heat lamination was performed under conditions of 3 Pa to obtain a substrate (unexposed substrate) having an unexposed solder resist layer.

The evaluation results are shown in Table 2.

  As shown in Table 2-1, it can be seen that in Examples 1 to 11, good developability can be obtained without reducing the touch drying property. Moreover, it turns out that it has the outstanding softness | flexibility in a cured film. In particular, in Examples 6 to 10 containing a blocked isocyanate and a thermosetting component, it is excellent in solder heat resistance, electroless gold plating resistance, and electrical characteristics, and is useful as an alkali-developable photocurable resin composition. Recognize.

  On the other hand, as shown in Table 2-2, in the case of Comparative Example 1 using A-6 having the number of nuclei of 1, sufficient dryness to touch, solder heat resistance, and electroless gold plating resistance cannot be obtained. It was. Furthermore, in Comparative Example 2, diethylene glycol as A-7 volatilized during the drying step, and the characteristics could not be exhibited, and the developability was inferior as in Comparative Example 4.

Claims (15)

An alkali-developable photocurable resin composition comprising a hydroxyl group-containing resin represented by the general formula (I), a carboxyl group-containing resin, and a photopolymerization initiator.

(In the formula, R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, which may be the same or different, and R ² is an alkyl group having 1 to 10 carbon atoms or an alkylene group having 1 to 10 carbon atoms. And at least one functional group selected from the group consisting of a phenylene group, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Represents a group, p represents an integer of 1 to 5, q represents an integer of 2 or more, m represents an integer of 1 to 4, and n represents an integer of 1 to 10).   The photo-curing property according to claim 1, wherein the hydroxyl group-containing resin is a compound obtained by reacting a cyclic ether compound or a cyclic carbonate compound with a compound having two or more phenolic hydroxyl groups in one molecule. Resin composition.   The photocurable resin composition according to claim 2, wherein the softening point of the compound having two or more phenolic hydroxyl groups in one molecule is room temperature or higher.   The photocurable resin composition according to any one of claims 1 to 3, further comprising a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule.   Furthermore, a urethanization catalyst is contained, The photocurable resin composition of any one of Claims 1-4 characterized by the above-mentioned.   Furthermore, a thermosetting component is contained, The photocurable resin composition of any one of Claims 1-5 characterized by the above-mentioned.   Furthermore, a coloring agent is contained, The photocurable resin composition of any one of Claims 1-6 characterized by the above-mentioned.   Hardened | cured material obtained by apply | coating the photocurable resin composition of any one of Claims 1-7 on a base material, and making it photocure.   The cured product according to claim 8, wherein the base material is a copper layer.   The cured product according to claim 8 or 9, wherein the applied photocurable resin composition is photocured in a pattern.   The photocurable dry film obtained by apply | coating the photocurable resin composition of any one of Claims 1-7 to a carrier film, and making it dry.   The hardened | cured material obtained by sticking the photocurable dry film of Claim 11 on a base material, and making it photocure.   The cured product according to claim 12, wherein the base material is a copper layer.   The cured product according to claim 12 or 13, wherein the pasted photocurable dry film is photocured in a pattern.   A printed wiring board provided with the hardened | cured material of any one of Claims 8-14.