JP2016206216A - Curable resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition that is less likely to cause decrease in optical characteristics such as sensitivity and resolution by long-term storage even when the curable resin composition contains an oxime ester-based photopolymerization initiator.SOLUTION: The curable resin composition comprises (A) an alkali-soluble resin, (B) an oxime ester-based photopolymerization initiator, (C) a coupling agent, and (D) a solvent.SELECTED DRAWING: None

Description

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

  A curable resin composition is used as a material such as a solder resist used for forming a printed wiring board. As one of the components of such a curable resin composition, an oxime ester photopolymerization initiator has been conventionally used (for example, Patent Document 1).

JP 2011-022328 A

  The oxime ester-based photopolymerization initiator is a component that can also be used for a curable resin composition used for high-definition materials that require high sensitivity (for example, Patent Document 1), while oxime ester-based light. It was found that a curable resin composition containing a polymerization initiator gradually deteriorates optical properties such as sensitivity and resolution during storage. Further, due to such deterioration of optical characteristics over time, it has been difficult to provide a curable resin composition having excellent optical characteristics even after long-term storage.

  Accordingly, an object of the present invention is to provide a curable resin composition that is less susceptible to deterioration in optical properties such as sensitivity and resolution due to long-term storage, even for a curable resin composition containing an oxime ester photopolymerization initiator, An object of the present invention is to provide a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and a printed wiring board having the cured product.

  As a result of intensive studies in view of the above, the present inventors have found that the above-described problems can be solved by using an oxime ester photopolymerization initiator and a coupling agent together, and have completed the present invention.

  That is, the curable resin composition of the present invention comprises (A) an alkali-soluble resin, (B) an oxime ester photopolymerization initiator, (C) a coupling agent, and (D) a solvent. Is.

  The dry film of the present invention is characterized by having a resin layer obtained by applying the curable resin composition to a film and drying it.

  The cured product of the present invention is obtained by curing the curable resin composition or the resin layer of the dry film.

  The printed wiring board of this invention has the said hardened | cured material, It is characterized by the above-mentioned.

  The preservation | save method of this invention is a preservation | save method of the composition containing (B) oxime ester system photoinitiator, Comprising: (C) A coupling agent is mix | blended with the said composition, It is characterized by the above-mentioned. .

  According to the present invention, even in a curable resin composition containing an oxime ester-based photopolymerization initiator, a curable resin composition that is less likely to cause deterioration in optical properties such as sensitivity and resolution due to long-term storage, the composition A dry film having a resin layer obtained from the product, a cured product of the composition or the resin layer of the dry film, and a printed wiring board having the cured product can be provided.

  The curable resin composition of the present invention comprises (A) an alkali-soluble resin, (B) an oxime ester photopolymerization initiator, (C) a coupling agent, and (D) a solvent. is there.

  (D) About the solvent, in the resin composition used for the solder resist etc. used for a printed wiring board, it is generally known to mix | blend a solvent as a diluent, and especially the compound which has an ester bond is a solvent. As a general purpose. The present inventors, in the presence of such an ester solvent, gradually inactivates the oxime ester photopolymerization initiator, and the optical characteristics such as sensitivity and resolution after long-term storage are significantly reduced. Found out what happens. According to the present invention, by blending the (C) coupling agent, it is difficult to cause a decrease in optical characteristics, and a curable resin composition having excellent optical characteristics is obtained regardless of the type of solvent used. be able to.

  In addition, it is preferable to use an ether solvent as the solvent (D) because the optical characteristics are less likely to deteriorate due to long-term storage.

  Although many epoxy resins that are thermosetting components are liquefied by mixing with ester solvents or mixed solvents containing ester solvents, according to the present invention, such epoxy resins are commercially available. Even in the case of containing a curable resin composition, it is difficult to cause deterioration of optical characteristics due to long-term storage.

  By curing the curable resin composition of the present invention, a cured product excellent in gold plating resistance, acid resistance and alkali resistance can be obtained.

  The curable resin composition of the present invention may be stored in one liquid or in two or more liquids. When storing in two or more liquids, the method of dividing each component is not particularly limited, and the oxime ester-based photopolymerization initiator is either the first composition liquid (main agent) or the second composition liquid (curing agent). It may be included. For example, it can be divided into a first composition liquid (main agent) containing an alkali-soluble resin and a second composition liquid (curing agent) containing an oxime ester photopolymerization initiator. When storing two or more liquids for a long time, it is preferable to store the oxime ester photopolymerization initiator and the coupling agent in the same liquid. When storing in one liquid, it is preferable to store at a low temperature so that the curing reaction does not proceed.

  Hereinafter, the component which the curable resin composition of this invention contains is explained in full detail.

[(A) Alkali-soluble resin]
(A) It is preferable to use a carboxyl group-containing resin or a phenolic hydroxyl group-containing resin as the alkali-soluble resin. In particular, use of a carboxyl group-containing resin is more preferable from the viewpoint of developability.

  As the carboxyl group-containing resin, in particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is a photosensitive composition for performing alkali development, from the viewpoint of photocurability and development resistance. More preferred. The unsaturated double bond is preferably derived from acrylic acid, methacrylic acid, or derivatives thereof.

  As specific examples of the carboxyl group-containing resin, the following compounds (any of oligomers and polymers) are 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, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers Diol compounds such as polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups, and optionally one alcoholic hydroxyl group A carboxyl group-containing urethane resin obtained by a polyaddition reaction with a compound having an acid.

(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 ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound and a diol compound.

(4) During the synthesis of the resin of (2) or (3), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing photosensitive urethane resin.

(5) During the synthesis of the resin of the above (2) or (3), one isocyanate group and one or more (meth) acryloyl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal (meth) acrylate.

(6) A carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or higher polyfunctional epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group present in the side chain. Here, the epoxy resin is preferably solid. Hereinafter, this is referred to as carboxylic acid-modified epoxy acrylate. In addition, as a specific example of a polyfunctional epoxy resin, what was illustrated by paragraph 0039 of Unexamined-Japanese-Patent No. 2011-213828 is mentioned, for example.

(7) Carboxyl group-containing photosensitivity in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the resulting hydroxyl group. Resin. Here, the epoxy resin is preferably solid.

(8) Two bases such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are reacted with a dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid by reacting the bifunctional oxetane resin. A carboxyl group-containing polyester resin to which an acid anhydride is added.

(9) Bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes, etc. An unsaturated group-containing monocarboxylic acid to the reaction product obtained by reacting a compound having a reactive hydroxyl group with an alkylene oxide such as ethylene oxide or propylene oxide, and reacting the resulting reaction product with a polybasic acid anhydride A carboxyl group-containing photosensitive resin obtained by causing the reaction to occur.

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

(11) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid.

(12) In addition to the resins (1) to (11) above, one epoxy group and one or more (meth) acryloyl groups in one molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate A carboxyl group-containing photosensitive resin obtained by adding a compound having the following.

  In addition, in this specification, (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

  In the curable resin composition of the present invention, the carboxyl group-containing resin is preferably a resin obtained by combining the above (6) and (12). Specifically, the carboxylic acid-modified epoxy acrylate, the epoxy group, and the radical polymerizable property. It is preferable that it is (A1) carboxyl group-containing photosensitive resin obtained by making the compound which has an unsaturated group react.

Since the carboxyl group-containing resin as described above has many carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
Moreover, the acid value of the said carboxyl group-containing resin has the preferable range of 20-200 mgKOH / g, More preferably, it is the range of 40-150 mgKOH / g. When the acid value of the carboxyl group-containing resin is 20 mgKOH / g or more, the adhesion of the coating film becomes good and the alkali developability becomes good. On the other hand, when the acid value is 200 mgKOH / g or less, the dissolution of the exposed part by the developer can be suppressed, so that the line is thinner than necessary, or in some cases, the developer without distinguishing between the exposed part and the unexposed part It is possible to satisfactorily draw a patterned resist by suppressing dissolution and peeling.

  Moreover, although the weight average molecular weight of the said carboxyl group-containing resin changes with resin frame | skeletons, the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight is 2,000 or more, the tack-free performance is good, the moisture resistance of the coated film after exposure is good, the film loss during development can be suppressed, and the resolution can be suppressed. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is also excellent.

  A carboxyl group-containing resin may be used alone or in combination of two or more. When the curable resin composition of this invention contains 2 or more types of carboxyl group-containing resin, it is preferable to contain (A1) carboxyl group-containing photosensitive resin mentioned above, for example.

  In another embodiment, the curable resin composition of the present invention includes, as a carboxyl group-containing resin, the above-described (A1) carboxyl group-containing photosensitive resin and a carboxyl group-containing acrylic copolymer having no alicyclic skeleton. It may contain a coalescence. Examples of the carboxyl group-containing acrylic copolymer having no alicyclic skeleton include (1) styrene copolymer type carboxyl group-containing resins mentioned as specific examples of the carboxyl group-containing resin. As a compounding ratio in the case of compounding a carboxyl group-containing acrylic copolymer having no alicyclic skeleton, when the total carboxyl group-containing resin is 100 parts by mass, for example, 10 to 95 parts by mass, preferably 10 to 80 parts by mass.

  The phenolic hydroxyl group-containing resin is not particularly limited as long as it has a phenolic hydroxyl group, that is, a hydroxyl group bonded to a benzene ring, in the main chain or side chain. Preferably, it is a compound having two or more phenolic hydroxyl groups in one molecule. Examples of the compound having two or more phenolic hydroxyl groups in one molecule include catechol, resorcinol, hydroquinone, dihydroxytoluene, naphthalenediol, t-butylhydroquinone, t-butylhydroquinone, pyrogallol, phloroglucinol, bisphenol A and bisphenol F. Bisphenol S, biphenol, bixylenol, novolac-type phenol resin, novolac-type alkylphenol resin, bisphenol A novolak resin, dicyclopentadiene-type phenol resin, Xylok-type phenol resin, terpene-modified phenol resin, polyvinylphenols, phenol Of 1-naphthol or 2-naphthol with aromatic aldehydes It can be mentioned condensates but not limited thereto. A phenolic hydroxyl group containing compound can be used individually by 1 type or in combination of 2 or more types.

  (A) The compounding quantity of alkali-soluble resin is 10-95 mass% in conversion of solid content per curable resin composition, for example, Preferably, it is 10-80 mass%.

[(B) Oxime ester photopolymerization initiator]
(B) As the oxime ester photopolymerization initiator, an oxime ester photopolymerization initiator containing a structural portion represented by the following general formula (I) is preferable, and further an oxime ester photopolymerization initiator having a carbazole structure is used. An agent is more preferable. A dimeric oxime ester photopolymerization initiator may be used as the oxime ester photopolymerization initiator having the carbazole structure.

In general formula (I), R ¹ represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group. R ² represents a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group.

The phenyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom.
The alkyl group represented by R ¹ and R ² is preferably an alkyl group having 1 to 20 carbon atoms, and may contain one or more oxygen atoms in the alkyl chain. Further, it may be substituted with one or more hydroxyl groups.
The cycloalkyl group represented by R ¹ and R ² is preferably a cycloalkyl group having 5 to 8 carbon atoms.
The alkanoyl group represented by R ¹ and R ² is preferably an alkanoyl group having 2 to 20 carbon atoms.
The benzoyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms and a phenyl group.

  Examples of the oxime ester-based photopolymerization initiator including the structural portion represented by the general formula (I) include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], Compound represented by formula (I-1), 2- (acetyloxyiminomethyl) thioxanthen-9-one, and ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl]-, 1- (O-acetyloxime) and oxime ester compounds having a carbazole skeleton such as a compound represented by the following general formula (I-2).

In General Formula (I-2), R ¹¹ has the same meaning as R ¹ in General Formula (I), and R ¹² and R ¹⁴ each independently have the same meaning as R ² in General Formula (I). R ¹³ is 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 an alkoxy having 2 to 12 carbon atoms. A carbonyl group (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 has one or more oxygen atoms in the middle of the alkyl chain) Or a phenoxycarboxylic group.

  Such an oxime ester photopolymerization initiator is preferable because, for example, the sensitivity of the curable resin composition of the present invention can be increased with respect to exposure for direct imaging, and the resolution is excellent. The oxime ester photopolymerization initiator may be a dimer.

  The dimer oxime ester photopolymerization initiator is more preferably a compound represented by the following general formula (I-3).

In the general formula ^{(I-3), R 23} represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group, a naphthyl group. R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen group, a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, a benzofuryl group, or a benzothienyl group.
Ar is a single bond or an alkylene group having 1 to 10 carbon atoms, vinylene group, phenylene group, biphenylene group, pyridylene group, naphthylene group, anthrylene group, thienylene group, furylene group, 2,5-pyrrole-diyl group, It represents a 4,4′-stilbene-diyl group and a 4,2′-styrene-diyl group.
n represents an integer of 0 to 1.

The alkyl group represented by R ^23, preferably an alkyl group having 1 to 17 carbon atoms.
The alkoxy group represented by R ^23, preferably an alkoxy group having 1 to 8 carbon atoms.
The phenyl group represented by R ²³ may have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms) and an alkoxy group (preferably having 1 to 8 carbon atoms). ), An amino group, an alkylamino group (preferably an alkyl group having 1 to 8 carbon atoms) or a dialkylamino group (preferably an alkyl group having 1 to 8 carbon atoms).
The naphthyl group represented by R ²³ may have a substituent, and examples of the substituent include the same groups as the above-described substituent that the phenyl group represented by R ²³ may have.

The alkyl group represented by R ²¹ and R ²² is preferably an alkyl group having 1 to 17 carbon atoms.
As the alkoxy group represented by R ²¹ and R ²² , an alkoxy group having 1 to 8 carbon atoms is preferable.
The phenyl group represented by R ²¹ and R ²² may have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms) and an alkoxy group (preferably having a carbon number). 1-8), an amino group, an alkylamino group (preferably an alkyl group having 1 to 8 carbon atoms) or a dialkylamino group (preferably an alkyl group having 1 to 8 carbon atoms).
The naphthyl group represented by R ²¹ and R ²² may have a substituent, and the substituent is the same as the above substituent that the phenyl group represented by R ²¹ and R ²² may have. Groups.

Furthermore, in general formula (I-3), R ²¹ and R ²³ are each independently a methyl group or an ethyl group, R ²² is methyl or phenyl, and Ar is a single bond, a phenylene group, or a naphthylene. Group or thienylene group, n is preferably 0.

  As a compound represented by general formula (I-3), the following compound is more preferable.

  (B) As an oxime ester photoinitiator, CGI-325, Irgacure OXE01 (1.2-octanedione, 1- [4- (phenylthio)-, 2- (manufactured by BASF Japan Ltd.) are commercially available. O-benzoyloxime)]), Irgacure OXE02 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)), ADEKA N-1919, NCI-831, Changzhou Power Electronics New Materials Co., Ltd. TR-PBG-304, Nippon Chemical Industry Co., Ltd. TOE-04-A3, and the like.

  (B) An oxime ester photoinitiator can be used individually by 1 type or in combination of 2 or more types. The blending amount of the (B) oxime ester photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and still more preferably with respect to 100 parts by mass of the (A) alkali-soluble resin. Is a ratio of 0.1 to 5.0. (B) When the blending amount of the photopolymerization initiator is 0.01 parts by mass or more, the photocurability on copper becomes good, the coating film is difficult to peel off, and the coating properties such as chemical resistance are good. Become. On the other hand, when the compounding quantity of a photoinitiator (B) is 20 mass parts or less, the light absorption of (B) a photoinitiator becomes favorable and deep part curability improves.

  The curable resin composition of the present invention may contain other photopolymerization initiator. Examples of other photopolymerization initiators include known and commonly used compounds such as benzophenone, acetophenone, aminoacetophenone, benzoin ether, benzyl ketal, acylphosphine oxide, oxime ether, and titanocene.

  In order to improve the sensitivity to exposure, it is preferable to use an α-aminoacetophenone-based photopolymerization initiator containing a structural portion represented by the general formula (II) in combination.

In general formula (II), R ³ and R ⁴ each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group, and R ⁵ and R ⁶ each independently represent a hydrogen atom or a carbon number. 1 to 6 alkyl groups may be represented, or two may be bonded to form a cyclic alkyl ether group.

  As the α-aminoacetophenone photopolymerization initiator containing a structural moiety represented by the general formula (II), 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.

[(C) Coupling agent]
(C) As a coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, or the like can be used. Of these, silane coupling agents are preferred. The organic reactive groups possessed by the coupling agent include ethylenically unsaturated groups (unsaturated hydrocarbon groups) such as vinyl groups and acrylic groups, alkoxy groups, epoxy groups, amino groups, mercapto groups, isocyanate groups, imidazole groups, and thiazoles. Group, triazole group and the like, among which, at least one selected from an ethylenically unsaturated group (unsaturated hydrocarbon group), an epoxy group, an alkoxy group and a mercapto group is preferable.

  Silane coupling agents include trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetraproxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, dimethyldimethoxy Silane, diethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysila , Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane N-β- (aminoethyl) γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and the like.

  Titanium coupling agents include: tetraethoxy titanate, titanium alkoxides such as tetraisopropyl titanate and tetra-n-butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, polyhydroxy titanium stearate, titanium tetraacetylacetate Examples thereof include narate, polytitanium acetylacetonate, titanium octylene glycolate, titanium ethyl acetoacetate, titanium lactate, and titanium triethanolamate.

  As the zirconium-based and aluminum-based coupling agents, compounds corresponding to titanium-based compounds can be used.

  (C) A coupling agent can be used individually by 1 type or in combination of 2 or more types. (C) The compounding amount of the coupling agent is preferably 0.02 to 2.5% by mass, more preferably 0.06 to 1.3% by mass, based on the total amount of the curable resin composition (including the solvent). . When the blending amount of (C) the coupling agent is 0.02% by mass or more, the storage stability is excellent, and when it is 2.5% by mass or less, the developability becomes stable.

[(D) Solvent]
(D) As a solvent, it is preferable to use an organic solvent, for example, ketone solvents such as methyl ethyl ketone, cyclohexanone, methyl butyl ketone, methyl isobutyl ketone, and methyl ethyl ketone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene Solvent: cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (DPM), Ether solvents such as dipropylene glycol diethyl ether and tripropylene glycol monomethyl ether; ethyl acetate, Acid butyl, isobutyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, Ester solvents such as propylene carbonate; alcohol solvents such as ethanol, propanol, 2-methoxypropanol, n-butanol, isobutyl alcohol, isopentyl alcohol, ethylene glycol and propylene glycol; aliphatic hydrocarbon solvents such as octane and decane Petroleum ether, petroleum naphtha, hydrogenated naphtha, solvent naphtha, etc. Other agents such as, N, N-dimethylformamide (DMF), tetrachlorethylene, turpentine oil, and the like. In addition, Maruzen Petrochemical Co., Ltd. Swazol 1000, Swazol 1500, Standard Petroleum Osaka Sales Co., Ltd. Solvesso 100, Solvesso 150, Sankyo Chemical Co., Ltd. Solvent # 100, Solvent # 150, Shell Chemicals Japan Co., Ltd. Shell Sol A100, Shell Sol A150 Organic solvents such as Ipsol No. 100 and Ipsol No. 150 manufactured by Idemitsu Kosan Co., Ltd. may be used. (D) A solvent can be used individually by 1 type or in combination of 2 or more types. The combination of the solvent in the case of combining 2 or more types is not particularly limited, and examples thereof include a solvent containing an ether solvent and an ester solvent, a solvent containing an aromatic hydrocarbon solvent and an ester solvent, and the like.

  In the present invention, as described above, the solvent (D) is preferably an ether solvent, and even when an ester solvent is used, a curable resin composition that hardly deteriorates optical properties due to long-term storage. Can be obtained.

  The purpose of using the solvent is to dissolve the (A) alkali-soluble resin, dilute it, apply it as a liquid, and then temporarily dry it to form a film, thereby enabling contact exposure. The usage-amount of a solvent is not limited to a specific ratio, It can set suitably according to the coating method etc. to select.

(Curing component)
The curable resin composition of the present invention may contain a thermosetting component and a photocurable component as the curable component.

  The thermosetting component is contained for imparting heat resistance to the composition, and particularly preferably, two or more cyclic ether groups and cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in the molecule. And a thermosetting component having at least one of them. It has been confirmed that the use of a thermosetting component improves not only the heat resistance but also the adhesion to the substrate.

  Such a thermosetting component having two or more cyclic (thio) ether groups in the molecule has 2 or both of a 3, 4 or 5-membered cyclic ether group or a cyclic thioether group in the molecule. 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 oxetane compound, molecule Examples thereof include compounds having two or more thioether groups, that is, polyfunctional episulfide resins.

  Examples of the multifunctional epoxy compound include Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, and Epoto YD- 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, Sumitomo Epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); Epicoat YL903 manufactured by Mitsubishi Chemical Corporation, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., Dow Chemical D. E. R. 542, Sumitomo Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (all trade names); Epicoat 152 and Epicoat 154 manufactured by Mitsubishi Chemical Corporation, D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., EPPN-201, EOCN-1025, EOCN manufactured by Nippon Kayaku Co., Ltd. -1020, EOCN-104S, RE-306, Sumitomo Epoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Co., Ltd. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, Epicoat 807 manufactured by Mitsubishi Chemical Co., Ltd. Epototo YDF-170, YDF-175 manufactured by Toto Kasei Co., Ltd. -2004 etc. (all are trade names) bisphenol F type epoxy resins; Hydrogenated bisphenol A type epoxy resins such as Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Toto Kasei Co., Ltd .; Glycidylamine type epoxy resin such as Epicoat 604 made by Toto Kasei Co., Ltd., Epototo YH-434 made by Tohto Kasei Co., Ltd., Sumi-epoxy ELM-120 made by Sumitomo Chemical Co., Ltd. (all trade names); Hydantoin type epoxy resin; Alicyclic epoxy resin such as Celoxide 2021 (both trade names) Manufactured by Mitsubishi Chemical Corporation of YL-933, manufactured by Dow Chemical Company of T. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names) Type or biphenol type epoxy resin or a mixture thereof; Nippon Kayaku EBPS-200, ADEKA EPX-30, DIC EXA-1514 (trade name) and other bisphenol S type epoxy resins; Mitsubishi Chemical Bisphenol A novolak type epoxy resin such as Epicoat 157S (trade name); tetraphenylol ethane type epoxy resin such as Epicoat YL-931 (all trade names) manufactured by Mitsubishi Chemical; TEPIC manufactured by Nissan Chemical Industries, Ltd. ( (All are trade names) heterocyclic epoxy resins; Diglycidyl phthalate resin such as GT; Tetraglycidyl xylenoyl ethane resin such as ZX-1063 manufactured by Toto Kasei; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. HP-4032 manufactured by DIC, EXA Naphthalene group-containing epoxy resins such as -4750 and EXA-4700; epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; CP-50S and CP-50M manufactured by NOF Corporation Glycidyl methacrylate copolymer epoxy resin; Further, a copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; an epoxy-modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industries, Ltd.), a CTBN-modified epoxy resin (for example, YR-102 manufactured by Tohto Kasei Co., Ltd. YR-450, etc.) and the like, but not limited thereto.

  The polyfunctional epoxy compound may be a solid epoxy resin, a semisolid epoxy resin, or a liquid epoxy resin. Solid epoxy resins and semi-solid epoxy resins need to be diluted with a solvent, and in many cases a mixed solvent containing an ester solvent or an ester solvent is used, and the oxime ester photopolymerization initiator is remarkably deactivated. However, according to the present invention, even when at least one of a solid epoxy resin and a semi-solid epoxy resin is used, deterioration of optical characteristics due to long-term storage hardly occurs. In this specification, a solid epoxy resin refers to an epoxy resin that is solid at 40 ° C., and a semi-solid epoxy resin refers to an epoxy resin that is solid at 20 ° C. and is liquid at 40 ° C. Means an epoxy resin that is liquid at 20 ° C. Judgment of liquid state shall be made in accordance with the second “Liquid Confirmation Method” of the Ministerial Ordinance on Dangerous Goods Testing and Properties (Ministry of Local Government Ordinance No. 1 of 1989).

  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-type bisphenol S, calixarenes, calix resorcin arenes or etherified products such as the resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

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

  A thermosetting component can be used individually by 1 type or in combination of 2 or more types. The blending amount of the thermosetting component having two or more cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.8 equivalents relative to 1 equivalent of the alkali-soluble group of the alkali-soluble resin (A). More preferably, the range is 0.8 to 2.5 equivalents. By setting the blending amount within the above range, good heat resistance can be imparted to the cured product.

  As the photocurable component, a photopolymerizable monomer can be contained. Examples of the compound having one or more ethylenically unsaturated groups in the molecule used as the photopolymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, Acryloyl morpholine, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N -Dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, melamine (meth) acrylate, diethyleneglycol Di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, phenoxy Ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, glycerin diglycidyl ether di (meth) acrylate, glycerin triglycidyl ether tri (meth) acrylate, isobornyl (meth) acrylate, cyclopentadiene mono- Or di- (meth) acrylate; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolprop Polyvalent (meth) acrylates of polyhydric alcohols such as dipentaerythritol and tris-hydroxyethyl isocyanurate, or polyvalent (meth) acrylates of ethylene oxide or propylene oxide adducts of these polyhydric alcohols; And mono-, di-, tri- or more polyesters with hydroxyalkyl (meth) acrylates. These photopolymerizable monomers can be used alone or in combination of two or more.

  The amount of the photopolymerizable monomer is suitably in the range of 5 to 40 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. When the blending amount of the photopolymerizable monomer is 5 parts by mass or more, the photocurability imparting effect becomes better. On the other hand, when the amount is 40 parts by mass or less, the dryness to touch of the coating film is good.

(Inorganic filler)
The curable resin composition of the present invention preferably contains an inorganic filler because it is difficult for the optical characteristics to deteriorate due to longer storage. Moreover, you may mix | blend an inorganic filler in order to improve characteristics, such as adhesiveness of cured | curing material, mechanical strength, and a linear expansion coefficient. Examples of such fillers include known and commonly used materials such as barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder. The filler can be used. Of these, barium sulfate and silica are preferable. An inorganic filler can be used individually by 1 type or in combination of 2 or more types.

  The blending amount of the inorganic filler is preferably 10 to 500 parts by weight and more preferably 20 to 200 parts by weight with respect to 100 parts by weight of the (A) alkali-soluble resin. In this case, the viscosity of the composition is not excessively high, the coating property is good, and a cured product having excellent characteristics as a solder resist is obtained, which is preferable.

(Coloring agent)
The curable resin composition of the present invention can contain a colorant. As the colorant, for example, commonly known colorants such as red, blue, green, yellow, white and black 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. A coloring agent can be used individually by 1 type or in combination of 2 or more types.

(Other optional ingredients)
In the curable resin composition of the present invention, if necessary, known and usual polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, finely divided silica, organic bentonite, montmorillonite, etc. Known and commonly used thickeners, silicone-based, fluorine-based, polymer-based and other antifoaming agents and leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, Known and commonly used additives such as organic fillers, photopolymerization sensitizers, light stabilizers, dispersants, thermosetting catalysts, curing accelerators, flame retardants, flame retardant aids, and the like can be blended.

  The curable resin composition of the present invention is suitable for the formation of permanent coatings such as solder resists, coverlays, interlayer insulation layers, and etching resist films for printed wiring boards and flexible printed wiring boards. Therefore, it is suitable for forming a printed wiring board having a high density and a fine line. The patterning method is not particularly limited, but the curable resin composition of the present invention is also suitable for patterning by laser direct imaging such as h-ray direct imaging (HDI). The curable resin composition of the present invention includes printing ink, inkjet ink, photomask preparation material, printing proof preparation material, plasma display panel (PDP) partition, dielectric pattern, electrode (conductor circuit) pattern, electronic It can be used for production of shielding images of component wiring patterns, conductive pastes, conductive films, black matrices, and the like.

  The curable resin composition of this invention can be made into the form of the dry film obtained by apply | coating and drying on a film. Even in the form of a dry film, if the solvent remains, deactivation of the oxime ester photopolymerization initiator due to the solvent species may occur, but according to the present invention, as described above, the optical characteristics are deteriorated. It is possible to obtain a dry film that hardly occurs. When forming a dry film, the curable resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and is applied to a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater. It can be coated on a carrier film (support) with a gravure coater, spray coater, etc. to a uniform thickness, and usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes to form a dry coating film. Although there is no restriction | limiting in particular about a coating film thickness, Generally, the film thickness after drying is 0.1-100 micrometers suitably, It is suitably selected in 0.5-50 micrometers.

  As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 0.1-150 micrometers.

  In this case, it is preferable to laminate a peelable cover film on the surface of the coating film for the purpose of preventing dust from adhering to the surface of the coating film after forming the coating film on the carrier film. . As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used. When peeling the cover film, the adhesive force between the coating film and the cover film However, what is necessary is just to be smaller than the adhesive force of a coating film and a carrier film.

  In addition, after adjusting the curable resin composition of the present invention to a viscosity suitable for the coating method using the above solvent, on the substrate, dip coating method, flow coating method, roll coating method, bar coater method, screen printing Tack-free dry coating film by applying the organic solvent contained in the composition at a temperature of about 50 to 90 ° C. by volatile drying (temporary drying). Can be formed. The blending amount of the solvent after drying, that is, the ratio of the residual content of the solvent is preferably 0.1 to 4% by mass, based on the total amount of the resin layer of the dry film containing the solvent, and is 0.3 to 3% by mass. % Is more preferable. Moreover, in the case of the dry film which apply | coated the curable resin composition of this invention on the carrier film, dried and wound up as a film, this is so that the coating film of a composition may contact a base material with a laminator etc. After pasting on a base material, the layer of a coating film can be formed on a base material by peeling off a carrier film.

  These coating films can be photocured, for example, by irradiation with active energy rays, or can be cured by heating to a temperature of 100 to 250 ° C. to obtain a cured product.

  In addition to printed circuit boards and flexible printed circuit boards with pre-circuit formation, the base material is paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber. Copper graded laminates of all grades (FR-4 etc.) using materials such as epoxy, fluorine / polyethylene / polyphenylene ether, polyphenylene oxide / cyanate ester, etc. Examples thereof include a polyimide film, a PET film, a glass substrate, a ceramic substrate, and a wafer plate.

  Volatile drying performed after applying the curable resin composition of the present invention is performed in a dryer using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like equipped with a heat source of an air heating method using steam. It can carry out using the method of making a hot air counter-current contact, and the method of spraying on a support body from a nozzle.

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

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

  The preservation | save method of this invention is a preservation | save method of the composition containing (B) oxime ester system photoinitiator, Comprising: (C) A coupling agent is mix | blended with the said composition, It is characterized by the above-mentioned. . The composition may contain components other than (B) the oxime ester photopolymerization initiator and (C) the coupling agent, for example, the above components. (C) The composition containing the (B) oxime ester photopolymerization initiator in the presence of the coupling agent may be stored, and (C) the coupling agent is blended in the composition ( B) Before or after blending the oxime ester photopolymerization initiator into the composition.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to the following Example. In the following description, “parts” and “%” are all based on mass unless otherwise specified.

[Synthesis and preparation of alkali-soluble resin]
(Synthesis of carboxyl group-containing resin A-1)
Orthocresol novolak type epoxy resin [Dainippon Ink Chemical Industries, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6] 1070 g (number of glycidyl groups (aromatic ring)) Total number): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve.
Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. Into the obtained reaction liquid, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added, reacted at 110 ° C. for 4 hours, cooled, and photosensitive carboxyl A group-containing resin solution (referred to as varnish A-1) was obtained.
The resin solution (varnish A-1) thus obtained had a solid content of 65% and an acid value of the solid content of 89 mgKOH / g.

(Preparation of carboxyl group-containing resin A-2)
Cyclomer P (ACA) Z250 (solid content 45%, acid value 70.0 mgKOH / g) manufactured by Daicel Chemical Industries, Ltd. was used. Hereinafter, it is referred to as varnish A-2.

(Examples 1 to 12, Comparative Example 1; curable resin composition for permanent coating)
In accordance with the composition shown in the following table, each component is blended, premixed with a stirrer, dispersed with a three-roll mill, kneaded, and the first composition liquid (main agent) and the second composition liquid (cured) Agent). The compounding quantity in a table | surface shows a mass part.

Ａ−１：上記で合成して得たカルボキシル基含有樹脂溶液Ａ−１
Ｂ−１：イルガキュアＯＸＥ０２（オキシムエステル系光重合開始剤、ＢＡＳＦジャパン社製）
Ｂ−２：ＴＯＥ−０４−Ａ３（オキシムエステル系光重合開始剤、日本化学工業所社製)
Ｃ−１：ＫＢＭ−５１０３（アクリル基を有機反応基として含有するシランカップリング剤、信越シリコーン社製）
Ｃ−２：ＫＢＭ−３０３３（アルコキシ基を有機反応基として含有するシランカップリング剤、信越シリコーン社製）
Ｃ−３：ＫＢＭ−４０３（エポキシ基を有機反応基として含有するシランカップリング剤、信越シリコーン社製）
Ｃ−４：ＫＢＭ−８０３（メルカプト基を有機反応基として含有するシランカップリング剤、信越シリコーン社製）
Ｄ−１：カルビトールアセテート
Ｄ−３：ＤＰＭ（ジプロピレングリコ−ルメチルエーテル）
＊１：ＤＰＨＡ（ジペンタエリスリトールヘキサアクリレート、日本化薬社製）
＊３：ＫＳ−６６（信越シリコーン社製）
＊４：ジシアンジアミド（ＤＩＣＹ）
＊５：ＦＡＳＴＧＥＮ ＢＬＵＥ ５３８０（ＤＩＣ社製）
＊６：Ｂ−３０（硫酸バリウム、堺化学社製）
＊７：ｊＥＲ８２８（カルボキシル基を有するエポキシ樹脂、三菱化学社製)
＊８：メラミン (日産化学社製)

A-1: Carboxyl group-containing resin solution A-1 obtained by the above synthesis
B-1: Irgacure OXE02 (oxime ester photoinitiator, manufactured by BASF Japan)
B-2: TOE-04-A3 (oxime ester photopolymerization initiator, manufactured by Nippon Chemical Industry Co., Ltd.)
C-1: KBM-5103 (a silane coupling agent containing an acrylic group as an organic reactive group, manufactured by Shin-Etsu Silicone)
C-2: KBM-3033 (silane coupling agent containing an alkoxy group as an organic reactive group, manufactured by Shin-Etsu Silicone)
C-3: KBM-403 (a silane coupling agent containing an epoxy group as an organic reactive group, manufactured by Shin-Etsu Silicone)
C-4: KBM-803 (a silane coupling agent containing a mercapto group as an organic reactive group, manufactured by Shin-Etsu Silicone)
D-1: Carbitol acetate D-3: DPM (dipropylene glycol methyl ether)
* 1: DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)
* 3: KS-66 (manufactured by Shin-Etsu Silicone)
* 4: Dicyandiamide (DICY)
* 5: FASTGEN BLUE 5380 (DIC)
* 6: B-30 (barium sulfate, manufactured by Sakai Chemical Co., Ltd.)
* 7: jER828 (epoxy resin having a carboxyl group, manufactured by Mitsubishi Chemical Corporation)
* 8: Melamine (Nissan Chemical)

  About the obtained 1st composition liquid (main agent), 2nd composition liquid (curing agent), and Examples 1-12 obtained by mixing these and the curable resin composition of Comparative Example 1, according to the following And evaluated. The results are shown in the table below.

(Tackiness)
The photosensitive resin compositions of Examples and Comparative Examples were each coated on a patterned copper foil substrate by screen printing, dried for 30 minutes in a hot air circulating drying oven at 80 ° C., 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. The evaluation criteria are as follows. The obtained results are shown in Tables 3 and 4 below.
A: There is no stickiness.
○: There is no stickiness.
Δ: Some stickiness.
X: There is stickiness.

(Solder heat resistance)
The curable compositions of each Example and Comparative Example were applied on the entire surface of a patterned copper foil substrate by screen printing so that the dry film thickness was 20 μm, dried at 80 ° C. for 30 minutes, and then released to room temperature. Chilled. After exposing the pattern with an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp on this substrate, development was performed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 60 seconds. Got. This substrate was post-cured at 150 ° C. for 60 minutes to obtain a substrate on which a cured product pattern was formed. A rosin-based flux was applied to the substrate to obtain an evaluation substrate. The evaluation substrate was immersed in a solder bath set at 260 ° C. in advance and the flux was washed with denatured alcohol, and then the resist layer was visually observed and evaluated for swelling and peeling. The evaluation criteria are as follows. The results are shown in Tables 3 and 4 below.
○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more.
(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated 3 times or more.
X: The resist layer swells and peels off within 3 times for 10 seconds.

(Electrical insulation reliability)
The curable composition of each example and comparative example was applied on the entire surface by screen printing so that the dry film thickness was 20 μm on the substrate on which the comb-type electrode pattern of line / space = 50/50 μm was formed, and the temperature was 80 ° C. For 30 minutes and allowed to cool to room temperature. The substrate was exposed at an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp, and then developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 60 seconds to obtain a pattern. . This substrate was post-cured at 150 ° C. for 60 minutes to obtain an evaluation substrate on which a cured product pattern was formed, and then the insulation reliability (electrode corrosion property) was evaluated.
The evaluation method was that this comb-shaped electrode was 121 ° C., 97% R.D. H. A bias voltage of DC 30 V was applied under the heating and humidifying conditions, and the time until insulation deterioration was measured. Here, when the electric resistance value fell below 1 × 10 ⁶ Ω, it was determined that the insulation was deteriorated. The evaluation criteria are as follows. The results are shown in Tables 3 and 4 below.
◎: Time to insulation degradation is 300 hours or more ○: Time to insulation degradation is 200 hours to less than 300 hours △: Time to insulation degradation is 100 hours to less than 200 hours ×: Insulation degradation Less than 100 hours

(Gold plating resistance)
The curable compositions of each Example and Comparative Example were applied on the entire surface of a patterned copper foil substrate by screen printing so that the dry film thickness was 20 μm, dried at 80 ° C. for 30 minutes, and then released to room temperature. Chilled. After exposing the pattern with an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp on this substrate, development was performed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 60 seconds. Got. This substrate was post-cured at 150 ° C. for 60 minutes to obtain an evaluation substrate on which a cured product pattern was formed.
About the evaluation board | substrate, it plated on the conditions of nickel 5 micrometers and gold | metal | money 0.05 micrometer at 80-90 degreeC using the electroless nickel plating bath and electroless gold plating bath of a commercial item. In the plated evaluation substrate, the presence or absence of plating penetration was evaluated visually, and then the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows. The obtained results are shown in Tables 3 and 4 below.
A: No penetration was observed after plating, and no peeling occurred after tape peeling.
○: Slight penetration is observed after plating, but there is no peeling after tape peeling.
(Triangle | delta): Slight penetration is confirmed after plating, and it peels slightly after tape peeling.
X: Permeation was confirmed after plating, and peeling was also observed after tape peeling.

(Acid resistance)
The curable compositions of each Example and Comparative Example were applied on the entire surface of a patterned copper foil substrate by screen printing so that the dry film thickness was 20 μm, dried at 80 ° C. for 30 minutes, and then released to room temperature. Chilled. After exposing the pattern with an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp on this substrate, development was performed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 60 seconds. Got. This substrate was post-cured at 150 ° C. for 60 minutes to obtain an evaluation substrate on which a cured product pattern was formed.
The evaluation substrate was plated using a commercially available electroless nickel plating bath and electroless gold plating bath at 80 to 90 ° C. under the conditions of nickel 5 μm and gold 0.05 μm.
After the gold plating, after immersion in a 10 vol% H ₂ SO ₄ solution at 30 ° C. for 30 minutes, the presence or absence of plating penetration was evaluated visually, and the presence or absence of peeling of the resist layer was evaluated by tape peeling. The evaluation criteria are as follows. The obtained results are shown in Tables 3 and 4 below.
A: No penetration was observed, and there was no peeling after tape peeling.
○: Slight penetration is observed, but there is no peeling after tape peeling.
(Triangle | delta): A penetration is confirmed and peels slightly after tape peeling.
X: Permeation was confirmed, and peeling was also observed after tape peeling.

(Alkali resistance)
The curable compositions of each Example and Comparative Example were applied on the entire surface of a patterned copper foil substrate by screen printing so that the dry film thickness was 20 μm, dried at 80 ° C. for 30 minutes, and then released to room temperature. Chilled. After exposing the pattern with an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp on this substrate, development was performed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 60 seconds. Got. This substrate was post-cured at 150 ° C. for 60 minutes to obtain an evaluation substrate on which a cured product pattern was formed.
The evaluation substrate was plated using a commercially available electroless nickel plating bath and electroless gold plating bath at 80 to 90 ° C. under the conditions of nickel 5 μm and gold 0.05 μm.
The evaluation substrate after gold plating was immersed in a 10 wt% NaOH solution at 30 ° C. for 30 minutes, and then visually checked for the presence or absence of plating penetration, and then the presence or absence of peeling of the resist layer was observed by tape peeling. The evaluation criteria are as follows. The obtained results are shown in Tables 3 and 4 below.
A: No penetration was observed, and there was no peeling after tape peeling.
○: Slight penetration is observed, but there is no peeling after tape peeling.
(Triangle | delta): A penetration is confirmed and peels slightly after tape peeling.
X: Permeation was confirmed, and peeling was also observed after tape peeling.

(Developability)
The curable resin composition of each Example and Comparative Example was applied on the entire surface of the patterned copper foil substrate by screen printing so that the dry film thickness was 20 μm, dried at 80 ° C. for 30 minutes, and brought to room temperature. Allowed to cool. This substrate was developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 60 seconds to obtain a pattern. Using the obtained evaluation substrate, the state of the residue was visually confirmed and evaluated. The evaluation criteria are as follows. The obtained results are shown in Tables 3 and 4 below.
○: No residue.
Δ: There is a slight residue residue (filler residue).
X: Residue present.

(Resolution at the initial stage after production)
The curable resin compositions of each Example and Comparative Example were applied on the entire surface of a copper solid substrate by screen printing and dried at 80 ° C. for 30 minutes. Using a negative film of L / S = 50/500, the film was exposed at an optimum exposure amount, and developed with a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. under a spray pressure of 2 kg / cm ² for 60 seconds to obtain a pattern. . After development, the relief shape was observed with an optical microscope and evaluated as follows. The obtained results are shown in Tables 3 and 4 below.
(Double-circle): Neither the twist of the pattern, the thickness, nor the undercut (the dimensional difference between the top and the bottom) can be confirmed.
○: Some of twisting, fatness, and undercutting (difference between top and bottom) of the pattern was confirmed.
X: Any of clear, thick, and undercut (dimension difference between top and bottom) was confirmed.

(Resolution of 6 months after manufacture)
After the first composition liquid (main agent) and the second composition liquid (curing agent) were produced and stored at 20 to 25 ° C. (room temperature) and a humidity of 60% or less for 6 months, respectively, the obtained examples and The curable resin composition of the comparative example was applied on the entire surface of a copper solid substrate by screen printing and dried at 80 ° C. for 30 minutes. Using a negative film of L / S = 50/500, the film was exposed at an optimum exposure amount, and developed with a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. under a spray pressure of 2 kg / cm ² for 60 seconds to obtain a pattern. . After development, the relief shape was observed with an optical microscope and evaluated as follows. The obtained results are shown in Tables 3 and 4 below.
(Double-circle): Neither the twist of the pattern, the thickness, nor the undercut (the dimensional difference between the top and the bottom) can be confirmed.
○: Some of twisting, fatness, and undercutting (difference between top and bottom) of the pattern was confirmed.
X: Any of clear, thick, and undercut (dimension difference between top and bottom) was confirmed.

(Initial sensitivity after production)
The curable compositions of each Example and Comparative Example were coated on the washed copper solid substrate by screen printing so as to have a thickness of 10 μm after drying, and dried at 80 ° C. for 10 minutes in a hot air circulating drying oven. On this coating film, a step tablet (41 steps) made by Stouffer was applied, exposed at an exposure amount of 50 mJ / cm ² with an exposure machine equipped with a metal halide lamp made by Oak Manufacturing Co., Ltd., and 1 wt% Na ₂ CO ₃ aqueous solution. The number of remaining stages after developing for 1 minute at a spray pressure of 0.1 MPa was examined. The greater the number of remaining stages, the better the sensitivity and the better. The obtained results are shown in Tables 3 and 4 below.

(Sensitivity 6 months after manufacture)
After the first composition liquid (main agent) and the second composition liquid (curing agent) were produced and stored at 20 to 25 ° C. (room temperature) and a humidity of 60% or less for 6 months, respectively, the obtained examples and The entire surface of the curable resin composition of the comparative example was applied to a washed copper solid substrate by screen printing so as to have a thickness of 10 μm, and then dried at 80 ° C. for 10 minutes in a hot-air circulating drying oven. On this coating film, a step tablet (41 steps) made by Stouffer was applied, exposed at an exposure amount of 50 mJ / cm ² with an exposure machine equipped with a metal halide lamp made by Oak Manufacturing Co., Ltd., and 1 wt% Na ₂ CO ₃ aqueous solution. The number of remaining stages after developing for 1 minute at a spray pressure of 0.1 MPa was examined. The greater the number of remaining stages, the better the sensitivity and the better. The obtained results are shown in Tables 3 and 4 below.

(Storage stability (thickening))
The viscosity immediately after the production of the curable resin compositions of each Example and Comparative Example is taken as the initial value, and the viscosity of the curable resin composition after storage for 6 months at 20 to 25 ° C. (room temperature) and humidity of 60% or less after production. Thus, the thickening rate (%) was calculated by the following formula. As a viscosity, 0.2 ml of a sample was collected, and the viscosity of a 30-second value at 25 ° C. and a rotation speed of 5 rpm was measured using a cone plate viscometer (TV-33 manufactured by Toki Sangyo Co., Ltd.).
Thickening rate = (Viscosity after storage for 6 months at 20 to 25 ° C. and humidity of 60% or less / initial viscosity) × 100
The storage stability was evaluated as follows according to the value of the thickening rate. The obtained results are shown in Tables 3 and 4 below.
○: Less than 10% △: 10-30%
X: Greater than 30%

  It can be seen that the curable resin compositions of Examples 1 to 12 are excellent in sensitivity and resolution even after 6 months from manufacture. In contrast, it can be seen that the curable resin composition of Comparative Example 1 that does not contain a coupling agent has a marked decrease in sensitivity and resolution due to long-term storage.

(Example 13, Comparative Example 2; curable resin composition for etching resist)
In accordance with the composition shown in the following table, each component is blended, premixed with a stirrer, dispersed with a three-roll mill, kneaded, and the first composition liquid (main agent) and the second composition liquid (cured) Agent). The compounding quantity in a table | surface shows a mass part.

Ａ−２：上記で調整したカルボキシル基含有樹脂溶液Ａ−２
Ｂ−１：イルガキュアＯＸＥ０２（オキシムエステル系光重合開始剤、ＢＡＳＦジャパン社製）
Ｃ−３：ＫＢＭ−４０３（エポキシ基を有機反応基として含有するシランカップリング剤、信越シリコーン社製）
Ｄ−１：カルビトールアセテート
Ｄ−２：ＰＭＡ（プロピレングリコールモノメチルエーテルアセテート）
＊１：ＤＰＨＡ（ジペンタエリスリトールヘキサアクリレート、日本化薬社製）
＊２：イルガキュア３６９（α−アミノアルキルフェノン系光重合開始剤、ＢＡＳＦジャパン社製）
＊３：ＫＳ−６６（信越シリコーン社製）
＊５：ＦＡＳＴＧＥＮ ＢＬＵＥ ５３８０（ＤＩＣ社製）
＊７：メラミン (日産化学社製)

A-2: Carboxyl group-containing resin solution A-2 prepared as described above
B-1: Irgacure OXE02 (oxime ester photoinitiator, manufactured by BASF Japan)
C-3: KBM-403 (a silane coupling agent containing an epoxy group as an organic reactive group, manufactured by Shin-Etsu Silicone)
D-1: Carbitol acetate D-2: PMA (propylene glycol monomethyl ether acetate)
* 1: DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)
* 2: Irgacure 369 (α-aminoalkylphenone photopolymerization initiator, manufactured by BASF Japan)
* 3: KS-66 (manufactured by Shin-Etsu Silicone)
* 5: FASTGEN BLUE 5380 (DIC)
* 7: Melamine (Nissan Chemical)

  The obtained first composition liquid (main agent), second composition liquid (curing agent), and the curable resin compositions of Example 13 and Comparative Example 2 obtained by mixing these were evaluated as follows. Went. The results are shown in the table below.

(Developability)
The photosensitive resin composition of each example and comparative example was applied on the entire surface of the patterned copper foil substrate by screen printing so that the dry film thickness was 20 μm, dried at 80 ° C. for 30 minutes, and brought to room temperature. Allowed to cool. This substrate was developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 60 seconds to obtain a pattern. Using the obtained evaluation substrate, the state of the residue was visually confirmed and evaluated. The evaluation criteria are as follows. The obtained results are shown in Table 6 below.
○: No residue.
Δ: There is a slight residue residue (filler residue).
X: Residue present.

(Resolution at the initial stage after production, resolution at 6 months after production, initial sensitivity after production, sensitivity at 6 months after production and storage stability (thickening))
Evaluation was performed in the same manner as described above. The obtained results are shown in Table 6 below.

  It can be seen that the curable resin composition of Example 13 is excellent in sensitivity and resolution even after 6 months from manufacture. On the other hand, it can be seen that the curable resin composition of Comparative Example 2 containing no coupling agent has a significant decrease in sensitivity and resolution due to long-term storage.

Claims (5)

(A) an alkali-soluble resin,
(B) an oxime ester photopolymerization initiator,
(C) a coupling agent, and
(D) A curable resin composition comprising a solvent.   A dry film comprising a resin layer obtained by applying and drying the curable resin composition according to claim 1 on a film.   A cured product obtained by curing the curable resin composition according to claim 1 or the resin layer of the dry film according to claim 2.   A printed wiring board comprising the cured product according to claim 3. (B) A storage method for a composition containing an oxime ester-based photopolymerization initiator, wherein (C) a coupling agent is added to the composition.