KR101385857B1 - Photocurable resin composition, dry film and cured product thereof, and printed wiring board using the same - Google Patents

Abstract

(식 중, R¹은 (m+l)가의 다가 알코올 유도체를 나타내고, R²는 CH₂, C₂H₄, C₃H₆, C₄H₈, 치환 또는 비치환의 방향족환 중 어느 하나를 나타내고, R³은 치환 또는 비치환의 방향족환을 나타내고, m 및 n은 1 이상 10 미만의 정수이고, l은 0 또는 1 이상의 정수임)Even if it is a soldering resist cured film after ultraviolet-ray hardening and thermosetting, by the photocurable resin composition which can peel by aqueous alkali solution, and it becomes possible to reuse a board | substrate, the dry film and hardened | cured material obtained therefrom, and the said dry film and hardened | cured material Provided is a printed wiring board on which a cured film such as a solder resist is formed.
The photocurable resin composition excludes (A) poly (meth) acrylate which is conventionally used as a photosensitive component as needed except the poly (meth) acrylate derived from the compound containing the structure represented by following formula (1). Any one or two of (B) carboxylic acid resin, (C) poly (meth) acrylate and (D) epoxy resin, all derived from a compound including a structure represented by the following general formula (1). It contains in combination of species or more.
≪ Formula 1 >

(Wherein R ¹ represents a (m + l) valent polyhydric alcohol derivative, R ² represents CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , a substituted or unsubstituted aromatic ring R ³ represents a substituted or unsubstituted aromatic ring, m and n are an integer of 1 or more and less than 10, and l is 0 or an integer of 1 or more)

Description

Photocurable resin composition, its dry film, and hardened | cured material, and the printed wiring board using these {PHOTOCURABLE RESIN COMPOSITION, DRY FILM AND CURED PRODUCT THEREOF, AND PRINTED WIRING BOARD USING THE SAME}

The present invention is an alkali developable photocurable resin composition, a dry film and a cured product thereof, which can be peeled off by an aqueous alkali solution even if the solder resist cured film after UV curing and thermal curing can be reused, and printing using these. It relates to a wiring board.

In manufacturing a printed wiring board or the like, a solder resist cured film is formed on the surface of the substrate for the purpose of preventing solder from adhering to a portion where the protection of the conductor circuit or soldering is unnecessary. As a method of forming a soldering resist cured film, it prints in a pattern form by screen printing, hardens with ultraviolet rays or a heat, and forms a soldering resist cured film, and after apply | coating and drying a soldering resist composition on the board | substrate surface, it exposes in a pattern form. There exists a method of forming a soldering resist hardened | cured material by image development and a heat hardening.

In the process of forming a solder resist cured film as described above, defects often occur due to printing defects such as cratering and smearing during printing, mixing of foreign matters, generation of pinholes, misalignment during exposure, and the like. When the substrate is discarded due to a defect caused by the solder resist forming process, all the processes starting from the formation of the laminated board up to the formation of the conductor circuit, the perforation, the filling of the holes, and the like are unnecessary, leading to a decrease in the yield.

Then, the method of peeling a soldering resist cured film and reusing a board | substrate is proposed (for example, refer patent document 1).

Patent Literature 1 uses sodium hydroxide or potassium hydroxide and three kinds of a mixed solution of glycol ether and water having a chain length of 3 to 6 as a stripping solution, thereby peeling off the solder resist cured by ultraviolet irradiation to enable reuse of the substrate. Is proposed.

However, peeling described in the said patent document 1 is effective only about the hardened | cured material hardened | cured by ultraviolet irradiation, and it is impossible to peel off the hardened | cured material heat-hardened.

Moreover, even if it is a soldering resist cured film after hardening by ultraviolet irradiation or heat, the peeling liquid which peels and enables reuse of a board | substrate is also proposed (for example, refer patent document 2).

However, in the said patent document 2, an alkali metal hydroxide and an aprotic polar solvent (N-methyl- 2-pyrrolidone) are used as stripping solution, and it cannot be said that there is little load on an environment.

Japanese Patent Laid-Open No. 7-115048 (claims) Japanese Patent Laid-Open No. 11-145594 (claims)

This invention is made | formed in view of the prior art as mentioned above, Even if it is a soldering resist cured film after UV hardening and thermosetting, it is 10 to 60 minutes with alkaline aqueous solution, for example, 5-20 weight% sodium hydroxide aqueous solution of 60 degreeC. It aims at providing the photocurable resin composition and its dry film which can peel by processing to a degree and become able to reuse a board | substrate.

In particular, by using the photocurable resin composition containing the curable component derived from polyester as a main component as a soldering resist, providing the photocurable resin composition which can collect | recover the raw materials of polyester, such as terephthalic acid, from the waste liquid, and its dry film It is aimed.

Moreover, the objective of this invention is providing the printed wiring board which can peel a soldering resist cured film and reuses a board | substrate by using such a photocurable resin composition and its dry film.

In order to achieve the above object, according to the present invention, even if it is a cured film after ultraviolet curing and thermosetting, it can be peeled off by treating with alkali aqueous solution, for example, about 5 to 20 weight% of sodium hydroxide aqueous solution for about 60 to 60 minutes. A photocurable resin composition is provided, and according to one aspect thereof,

(A) poly (meth) acrylate (except poly (meth) acrylate derived from a compound containing a structure represented by the following formula (1)),

All containing one or two or more of (B) carboxylic acid resin, (C) poly (meth) acrylate, and (D) epoxy resin, all derived from a compound containing a structure represented by the following formula (1): A photocurable resin composition is provided.

(Wherein R ¹ represents a (m + l) valent polyhydric alcohol derivative, R ² represents CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , a substituted or unsubstituted aromatic ring R ³ represents a substituted or unsubstituted aromatic ring, m and n are an integer of 1 or more and less than 10, and l is 0 or an integer of 1 or more)

According to a preferred embodiment, any one or two or more of the carboxylic acid resins (B), poly (meth) acrylates (C) and epoxy resins (D) are contained in a ratio of 20% by weight or more with respect to the organic matter in the composition. do.

In addition, according to another aspect of the present invention, any of (B) carboxylic acid resin, (C) poly (meth) acrylate and (D) epoxy resin, all derived from a compound containing a structure represented by the formula (1) A photocurable resin composition is provided which contains 1 type, or 2 or more types by 20 weight% or more with respect to the organic substance in a composition.

In a preferred embodiment, in the above formula (1), R ¹ is a trivalent alcohol derivative, R ² is C ₂ H ₄ , and R ³ is preferably a benzene ring.

Moreover, according to this invention, the photocurable dry film obtained by apply | coating and drying the said photocurable resin composition on a film, the hardened | cured material obtained by hardening | curing the said photocurable resin composition or the said dry film, especially when obtained by photocuring on copper Hardened | cured material obtained by photocuring to a cargo or a pattern form is also provided.

Moreover, according to this invention, it has a cured film obtained by carrying out the photocuring of the said photocurable resin composition or a dry film in a pattern form, and then thermosetting, The printed wiring board also provided.

The curable resin or compound used in the photocurable resin composition of the present invention is a carboxylic acid resin, a poly (meth) acrylate or an epoxy resin derived from a compound containing a structure represented by the above formula (1). Therefore, since the ester bond which bear | maintains a main skeleton hydrolyzes by processing with aqueous alkali solution, and the carboxyl group and hydroxyl group which were produced by the said hydrolysis express strong hydrophilicity, it turns out that the formed cured film can be peeled off by aqueous alkali solution. The inventors have discovered. By using this action, for example, as a soldering resist composition, since the curable resin or compound used for the conventional soldering resist composition is a novolak-type epoxy resin or novolak-type epoxyacrylate, a main skeleton does not hydrolyze and peels off We could overcome this bad defect. Therefore, when a defect arises in the soldering resist cured film preparation process, it is possible to reuse a board | substrate by peeling the soldering resist of a board | substrate. In addition, unlike the conventional epoxy acrylate-modified resin, it is possible to use a raw material that does not contain halogen ions. Therefore, halogen-freeization is possible and the cured film excellent in electrical insulation, heat resistance, and a touch drying property can be formed.

Therefore, the photocurable resin composition of this invention can be advantageously applied to formation of the cured film, such as the soldering resist of a printed wiring board and a flexible printed wiring board.

Moreover, since the photocurable resin composition of this invention contains the curable component derived from polyester as a main component, raw material of polyester, such as terephthalic acid, can be collect | recovered from the waste liquid of the peeled solder resist, and also in terms of resource saving and environmental protection Very useful.

As mentioned above, the characteristic of the photocurable resin composition of 1 aspect of this invention is derived from the compound containing the structure represented by the formula (A) poly (meth) acrylate conventionally used as a photosensitive component (the following general formula (1). (B) carboxylic acid resin, (C) poly (meth) acrylate and (D) epoxy, all derived from a compound comprising a structure represented by the following general formula (1) It contains in any 1 type or in combination of 2 or more types of resin.

≪ Formula 1 >

(Wherein R ¹ represents a (m + l) valent polyhydric alcohol derivative, R ² represents CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , a substituted or unsubstituted aromatic ring R ³ represents a substituted or unsubstituted aromatic ring, m and n are an integer of 1 or more and less than 10, and l is 0 or an integer of 1 or more)

According to the research of the present inventors, when such a photocurable resin composition is used as a soldering resist, it has sufficient alkali resistance with respect to general treatment, such as immersing in 10weight% NaOH of 25 degreeC for 30 minutes, for example, and it is 60 degreeC By processing about 5 to 20 minutes with 5 to 20 weight% of NaOH aqueous solution, it discovered that the hardened soldering resist coating film can be peeled off, and it has come to complete this invention.

In addition, according to the studies of the present inventors, (B) carboxylic acid resin, (C) poly (meth) acrylate and (D) epoxy resin, all derived from a compound containing a structure represented by the formula (1), If it is 20 weight% or more with respect to the organic substance in a composition by any 1 type or 2 or more types of combination, another (A) poly (meth) acrylate other than the above (does not contain the structure represented by the said Formula (1), or the said Formula (1) It was found that the same effect can be obtained even if it does not contain poly (meth) acrylate derived from a compound which does not contain the structure represented by. However, (B) carboxylic acid resin, (C) poly (meth) acrylate, and (D) epoxy resin derived from the compound containing the structure represented by the said Formula (1) are any 1 type, or 2 or more types of combination It is preferable to mix | blend so that it may be 80 weight% or less with respect to the organic substance in a composition. When it mixes in large quantities beyond this ratio, since the alkali resistance of a cured coating film may fall, it is unpreferable. Moreover, it is advantageous in that it contains (A) poly (meth) acrylate other than poly (meth) acrylate derived from the compound containing the structure represented by the said Formula (1) in that optical characteristics, such as a sensitivity, are improved.

Hereinafter, each structural component of the photocurable resin composition of this invention is demonstrated in detail.

First, as the (A) poly (meth) acrylate used in the present invention, a poly (meth) acrylate derived from a compound which does not contain the structure represented by the formula (1) or does not contain the structure represented by the formula (1) All can be used and it is not limited to the specific polyfunctional (meth) acrylate. Specific examples include polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or ethylene oxide adducts thereof, propylene oxide adducts, or the like. polyvalent acrylates such as ε-caprolactone adduct; Polyfunctional acrylates such as phenoxy acrylate, bisphenol A diacrylate and ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; Not limited to the above, polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, and the like, and acrylates and melamine acrylates and / or the acrylates Each corresponding methacrylate etc. are mentioned.

In addition, in this specification, (meth) acrylate is a term which generically mentions acrylate, methacrylate, and mixtures thereof, and it is the same also about other similar expression.

The carboxylic acid resin (B) derived from the compound containing the structure represented by the formula (1) used in the present invention is obtained by reacting a polybasic acid or an anhydride thereof as described below with a compound containing the structure represented by the formula (1). Lose. Preferably, (a) is obtained by reacting (a) the polybasic acid or its anhydride simultaneously with or depolymerizing the (b) polyester with (b) a polyol having two or more hydroxyl groups in one molecule.

The (B) carboxylic acid resin may have a photosensitive group. In this case, what is necessary is just to make the compound containing the structure represented by the said General formula (1) react with the compound which has 1 or more ethylenically unsaturated group, polybasic acid, or its anhydride in a molecule | numerator as mentioned later. Preferably, (a) a compound having one or more ethylenically unsaturated groups in the molecule and (c) a polybasic acid in (b) simultaneously or depolymerizing (a) the polyester with (b) a polyol having two or more hydroxyl groups in one molecule. Or anhydrides thereof. The said (d) component and (c) component may be made to react collectively, or you may make it react sequentially. In the case of the sequential reaction, the order of reacting the component (d) may be reacted first, followed by the component (c), or the component (c) may be reacted first, and then the component (d) may be reacted. As mentioned above, Preferably, it is necessary to set it as the reaction rate which makes two or more carboxyl groups produce | generate.

The (C) poly (meth) acrylate derived from the compound containing the structure represented by the formula (1) used in the present invention is at least one ethylene in a molecule as described later in the compound containing the structure represented by the formula (1) It is obtained by making a compound which has a unsaturated unsaturated group react, or making a polybasic acid or its anhydride react, and making the reaction react with the compound which has 1 or more ethylenically unsaturated group in a molecule | numerator. Preferably, (a) reacting a compound having at least one ethylenically unsaturated group in the molecule (d) simultaneously with or depolymerizing (a) the polyester with (b) a polyol having two or more hydroxyl groups in one molecule, or It is obtained by making (c) polybasic acid or its anhydride react, and (d) reacting the compound with the compound which has 1 or more ethylenically unsaturated group in a molecule | numerator.

(D) The epoxy resin derived from the compound containing the structure represented by the formula (1) used in the present invention is to react epichlorohydrin to the compound containing the structure represented by the formula (1) or polybasic acid or anhydride thereof or It is obtained by reacting the compound which has a some epoxy group in epichlorohydrin or a molecule | numerator after processing with the monocarboxylic acid which has a phenol group. Preferably (a) the polymer is depolymerized into (b) a polyol having two or more hydroxyl groups in one molecule, and the resulting depolymer is reacted with epichlorohydrin as it is (c) polybasic acid or anhydride thereof or (e) It is obtained by reacting the compound which has a some epoxy group in epichlorohydrin or (f) molecule | numerator after processing with the monocarboxylic acid which has a phenol group.

The ratio of the polyol which has two or more hydroxyl groups in polyester and one molecule at the time of depolymerization of the said polyester is the mole number ((alpha)) of the repeating unit of polyester, and the number of moles ((beta)) of the polyol which has two or more hydroxyl groups in 1 molecule. The ratio of (α) / (β) = 0.5 to 3 is appropriate, preferably in the range of 0.8 to 2, preferably. When the said ratio is less than 0.5, since a polyol component is contained too much, the ratio of the aromatic ring derived from polyester decreases, and since the effect of improving heat resistance and chemical-resistance becomes less, it is unpreferable. On the other hand, when the said ratio is larger than 3, since depolymerization is crystallizing in most cases and it is insoluble in a solvent, it is not preferable.

The polyester (a) may be any conventionally known polyester, but polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, liquid crystal polymer, and the like may be used. have. In addition, recycled PET and recycled PET recovered from waste such as PET bottle waste can be used, and these are preferable from the viewpoint of environmental protection. Recovered PET can be crushed and washed, and recycled PET can be washed and pelletized on the market. Although the shape of the said polyester is not specifically limited, It is more preferable that it is a pellet form and / or a flake form. In addition, the fine powder does not need to be finely ground, but may be ground.

As a polyol which has two or more hydroxyl groups in said (b) 1 molecule, all can use bifunctional polyol, a trifunctional or more than trifunctional polyol, etc., and can be used individually or in combination of 2 or more types.

As the bifunctional polyol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, 1,3-butanediol and neopentyl Glycol, spiroglycol, dioxane glycol, adamantanediol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2-methylpropanediol Ethylene jade of bifunctional phenol such as 1,3, 3-methylpentanediol1,5, hexamethylene glycol, octylene glycol, 9-nonanediol, 2,4-diethyl-1,5-pentanediol, bisphenol A Seed modified compounds, propylene oxide modified compounds of bifunctional phenols such as bisphenol A, ethylene oxide of bisphenol A, propylene oxide copolymer modified compounds, copolymerized polyether polyols of ethylene oxide and propylene oxide, polycarbonate diol, Adamantanediol, Polyetherdiol, Polyesterdiol, Poly Prolactonediol (e.g., Plaxel 205, Plaxel L205AL, Plaxel 205U, Plaxel 208, Plaxel L208AL, Plaxel 210, Plaxel 210N, Plaxel 212, Plaxel L212AL, Plaxel 220, Plaxel) 220N, Flaccel 220NP1, Flaccel L220AL, Flaccel 230, Flaccel 240, Flaccel 220EB, Flaccel 220EC; The above are all manufactured by Daicel Chemical Co., Ltd .; trade name), hydroxyl group terminal polyalkane dienediol ( Elastomers such as 1,4-polyisoprendiol, 1,4- and 1,2-polybutadienediol and their hydrogenated materials), for example, of the hydroxyl group-terminated polyalkanedienediol Examples of commercially available products include Epol (registered trademark; hydrogenated polyisoprendiol, molecular weight 1,860, average degree of polymerization 26, manufactured by Idemitsukosan Co., Ltd.), PIP (polyisoprendiol, molecular weight 2,200, average degree of polymerization 34, manufactured by Idemitsukosan Co., Ltd.), poly Tail (registered trademark) H (hydrogenated polybutadienediol, molecular weight 2,200, square Homopolymerization degree 39, Mitsubishi Chemical Co., Ltd. make, R-45HT (polybutanediol, molecular weight 2,270, average degree of polymerization 42, Idemitsukosan Co., Ltd. product), etc. are mentioned.

As a trifunctional or more than trifunctional polyol, glycerin, trimethylol ethane, trimethylol propane, sorbitol, pentaerythritol, ditrimethylol propane, dipentaerythritol, tripentaerythritol, adamantane triol, and polycaprolactone triol (e.g., For example, as the ones having Flaccel 303, Flaccel 305, Flaccel 308, Flaccel 312, Flaccel L312AL, Flaccel 320ML, Flaccel L320AL; all of the above are manufactured by Daicel Chemical Co., Ltd .; Examples of the compound having an ethylene oxide, a propylene oxide modified product, and a heterocycle of a trifunctional or higher functional phenol compound include a Shikoku Chemical Co., Ltd. make and the like. In particular, when trimethylolpropane is used, it is preferable to have an amorphous semi-solid fluidity that does not become cloudy when the depolymerized product is used, and solubility in a solvent is increased.

As said (c) polybasic acid or its anhydride, a conventionally well-known polybasic acid or its anhydride can be used. Specific examples thereof include aromatic polyhydric carboxylic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, tetrabromphthalic anhydride, methylhymic anhydride and tetrachlorophthalic anhydride and anhydrides thereof, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, 1,4- Alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and anhydrides thereof, aliphatic acids such as maleic anhydride, fumaric acid, succinic anhydride, adipic acid, sebacic acid, and azelaic acid Polyfunctional carboxylic acids and trifunctional or higher functional carboxylic acids such as anhydrides thereof, pyromellitic anhydride, trimellitic anhydride, methylcyclohexenedicarboxylic acid anhydride, and the like, and the like, or a combination of two or more thereof. Can be used.

Examples of the compound having at least one ethylenically unsaturated group in the above (d) molecule include a compound having one carboxyl group and at least one ethylenically unsaturated group, a (meth) acrylic monomer having an isocyanate group, one cyclic ether group and at least one ethylenic group. The compound which has an unsaturated group, the compound which has one hydroxyl group and one or more ethylenically unsaturated group, etc. are mentioned, It can be used individually or in combination of 2 or more types.

Examples of the compound having one carboxyl group and one or more ethylenically unsaturated groups include acrylic acid, dimers of acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfuryl acrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, (Meth) acrylic-acid caprolactone addition product, the half-ester compound of the (meth) acrylate which has one hydroxyl group in saturated or unsaturated dibasic acid anhydride, and one molecule, etc. are mentioned. As (meth) acrylate which has a hydroxyl group for manufacturing a half ester compound, For example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylol Propanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenylglycidyl (meth) acrylate and the like. Examples of the dibasic acid anhydride for producing the half ester compound include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl endmethylene tetrahydrophthalic anhydride, and the like. These can be mentioned individually or in combination of 2 or more types.

The (meth) acrylic monomer having an isocyanate group may be any isocyanate compound having one isocyanate group and one or more ethylenically unsaturated groups in one molecule, and is not particularly limited. As a specific example, (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxyethoxyethyl isocyanate, bis (acryloxymethyl) ethyl isocyanate, these modified bodies, etc. are mentioned, for example, individually or 2 It can use combining a species or more. As a commercial item, "Karenz MOI" (methacryloyloxyethyl isocyanate), "Karenz AOI" (acryloyloxyethoxyethyl isocyanate), "Karenz MOI-EG" (methacryloyloxyethoxyethyl isocyanate) ), "Karens MOI first BM" (isocyanate block body of Karenz MOI), "Karens MOI-BP" (isocyanate block body of Karenz MOI), "Karens BEI" (1,1-bis (acryloxy Methyl) ethyl isocyanate) is commercially available from Showa Denko. All these trade names are registered trademarks. Moreover, the half-urethane compound of the compound which has one hydroxyl group and one or more ethylenically unsaturated group in 1 molecule, and diisocyanate, such as isophorone diisocyanate, toluylene diisocyanate, tetramethyl xylene diisocyanate, hexamethylene diisocyanate, can also be used. Can be.

As a compound which has one cyclic ether group and one or more ethylenically unsaturated groups in 1 molecule, 2-hydroxyethyl (meth) acrylate glycidyl ether, 2-hydroxypropyl (meth) acrylate glycidyl ether, 3-hydroxypropyl (meth) acrylate glycidyl ether, 2-hydroxybutyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-hydroxypentyl (Meth) acrylate glycidyl ether, 6-hydroxyhexyl (meth) acrylate glycidyl ether or glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl acrylate, etc. are mentioned, It can be used individually or in combination of 2 or more types.

As a compound which has the said hydroxyl group and ethylenically unsaturated group, what is necessary is just a compound which has one hydroxyl group and 1 or more ethylenically unsaturated group in 1 molecule, and is not specifically limited. Specific examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, di Hydroxyalkyl (meth) acrylates, such as pentaerythritol penta (meth) acrylate, are mentioned, It can be used individually or in combination of 2 or more types.

The (meth) acrylic monomer having a functional group capable of reacting with an alcohol or carboxylic acid as described above may be used alone or in combination of two or more thereof.

Examples of the monocarboxylic acid having the phenol group (e) include 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-amino-3-hydroxyphenylpropionic acid, 3,4-dihydroxyphenylalanine, 3,4,5-trihydroxybenzoic acid, etc. can be mentioned, It can be used individually or in combination of 2 or more types.

As a compound which has a some epoxy group in the said (f) molecule | numerators, it is adecaizer O-130P by the Adeka company, adecaizer O-180A, adecaizer D-32, adecaizer D-55, etc. Epoxidized vegetable oils; JER (registered trademark) 828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, EHPE3150 manufactured by Daicel Chemical Industries, Ltd., Epiclone (registered trademark) 840 manufactured by DIC Corporation, Epiclone 850, Epiclone 1050, Epiclone 2055, Efototo (registered trademark) YD-011, YD-013, YD-127, YD-128, DER317, DER331, DER661, DER664, BASF made by Shinnitetsu Chemical Co., Ltd. (BASF) Araldite 6071, Araldite 6084, Araldite GY250, Araldite GY260, Sumitomo Epoxy ESA-011, ESA-014, ELA-115, ELA-128 made by Sumitomo Chemical Co., Ltd. Bisphenol A type epoxy resins, such as AER330, AER331, AER661, AER664 by Asahi Kasei Kogyo Co., Ltd. (all are brand names); JERYL903 manufactured by Mitsubishi Chemical Corporation, Epiclone 152 manufactured by DIC Corporation, Epiclone 165, Efototo YDB-400, YDB-500 manufactured by Shinnitetsu Chemical Co., Ltd., DER542 manufactured by Dow Chemical, manufactured by BASF Japan Brominated epoxy resins such as Araldite 8011, Sumitomogagaku Kogyo Co., Ltd. Sumi-Epoxy ESB-400, ESB-700, and Asahi Kasei Kogyo AER711, AER714 (both trade names); JER152, jER154 made by Mitsubishi Chemical Co., Ltd., DEN431, DEN438 made by Dow Chemical Company, epiclon N-730, epiclon N-770 made by DIC company, epiclon N-865, made by Shinnitetsu Chemical Co., Ltd. Efototo YDCN-701, YDCN-704, Araldite ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307 by BASF Japan, EPPN (registered trademark) -201 by Nippon Kayaku Co., Ltd., EOCN (Registered trademark) -1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumi-Epoxy ESCN-195X, ESCN-220, AERECN- made by Sumitomo Chemical Co., Ltd. Novolak-type epoxy resins, such as 235 and ECN-299 (all are brand names); Epiclon 830 manufactured by DIC Corporation, jER807 manufactured by Mitsubishi Chemical Corporation, Efototo YDF-170, YDF-175, YDF-2004 manufactured by Shinnitetsu Chemical Co., Ltd., Araldite XPY306 manufactured by BASF Japan Corporation, etc. (all Bisphenol F type epoxy resin; Hydrogenated bisphenol A epoxy resins, such as Efototo ST-2004, ST-2007, ST-3000 (brand name) by Shin-Nitetsu Chemical Co., Ltd .; JER604 manufactured by Mitsubishi Chemical Corporation, Efototo YH-434 manufactured by Shinnitetsu Chemical Corporation, Araldite MY720 manufactured by BASF Japan Corporation, Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (all brand names) Glycidyl amine epoxy resins; Hydantoin type epoxy resins, such as Araldite CY-350 (brand name) by BASF Japan company; Alicyclic epoxy resins such as Celoxide (registered trademark) 2021 manufactured by Daicel Chemical Industries, Ltd., Araldite CY175 manufactured by BASF Japan Co., Ltd. (CY179, etc.); A trihydroxyphenylmethane type epoxy resin such as YL-933 manufactured by Mitsubishi Chemical Corporation, T.E.N., EPPN-501, and EPPN-502 manufactured by Dow Chemical Co. (all trade names); Biscylenol-type or biphenol-type epoxy resins such as YL-6056, YX-4000 and YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation; Bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Adeka Co., and EXA-1514 (trade name) manufactured by DIC Corporation; A bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; Tetraphenylolethane type epoxy resins such as jERYL-931 manufactured by Mitsubishi Chemical Co., Ltd. and Araldite 163 manufactured by BASF Japan Corporation; Heterocyclic epoxy resins such as Araldite PT810 (trade name) manufactured by BASF Japan Co., Ltd. and TEPIC (registered trademark) manufactured by Nissan Chemical Industries, Ltd .; Diglycidyl phthalate resins such as Bremmer (registered trademark) DGT manufactured by Nippon Yushi Corporation; Tetraglycidyl xylenoylethane resins such as ZX-1063 manufactured by Shinnitetsu Chemical Co., Ltd .; Naphthalene-group containing epoxy resins, such as Shinnitetsu Chemical Co., Ltd. ESN-190, ESN-360, and DIC Corporation HP-4032, EXA-4750, EXA-4700; Epoxy resins having a dicyclopentadiene skeleton, such as HP-7200 and HP-7200H manufactured by DIC Corporation; Glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M manufactured by Nippon Yushi Co., Ltd .; A copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy modified polybutadiene rubber derivatives (for example, Daicel Chemical Co., Ltd. PB-3600, etc.), CTBN modified epoxy resins (for example, Shinnitetsu Chemical Co., Ltd. YR-102, YR-450, etc.) etc. are mentioned. However, it is not limited to these. Among them, an epoxy resin that does not use epichlorohydrin in the process of epoxidation, or an epoxy resin having high purity and low amount of residual chlorine is preferable from the viewpoint of halogen-free. These epoxy resins may be used alone or in combination of two or more.

In order to promote the depolymerization, a depolymerization catalyst may be used. Examples of the depolymerization catalyst include monobutyltin hydroxide, dibutyltin oxide, monobutyltin-2-ethylhexanoate, dibutyltin dilaurate, tin oxide, tin acetate, zinc acetate, manganese acetate, Cobalt acetate, calcium acetate, lead acetate, antimony trioxide, tetrabutyl titanate, and tetraisopropyl titanate. As for the usage-amount of these depolymerization catalysts, the range of 0.005-5 mass parts normally, Preferably it is 0.05-3 mass parts with respect to 100 mass parts of total amounts of the said polyester and polyhydric alcohol.

As the photoinitiator used in the present invention, at least one photoinitiator selected from the group consisting of an oxime ester photoinitiator having an oxime ester group, an α-aminoacetophenone photoinitiator, and an acylphosphine oxide photoinitiator can be preferably used. have.

As said oxime ester photoinitiator, CGI-325 by the BASF Japan company, Irgacure (registered trademark) OXE01, Irgacure OXE02, Adeka N-1919, NCI-831, etc. are mentioned as a commercial item. Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used preferably, Specifically, the oxime ester compound which has a carbazole structure represented by a following formula is mentioned.

(Wherein X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, An alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group having 1 to 8 carbon atoms) Y and Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 8 carbon atoms, An alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 8 carbon atoms, Substituted with an alkoxy group, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group), an anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, and Ar is a bond or 1 carbon atom. Alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-stilbene -Diyl, 4,2'-styrene-diyl, p is an integer of 0 or 1)

In particular, X and Y in the above formula are each methyl or ethyl, Z is methyl or phenyl, p is 0, and Ar is a bond or phenylene, naphthylene, thiophene or thienylene.

It is preferable that the compounding quantity of such an oxime ester system photoinitiator shall be 0.02-10 weight% of the whole composition. If it is less than 0.02 weight%, the photocurability on copper will run short, and a coating film will peel, and coating film characteristics, such as chemical resistance, will fall. On the other hand, when it exceeds 10 weight%, light absorption in the coating film surface becomes severe and there exists a tendency for deep-curing property to fall.

Specifically as said (alpha)-amino acetophenone type photoinitiator, 2-methyl-1- [4- (methylthio) phenyl] -2- morpholino propanone- 1, 2-benzyl-2- dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Butanone, N, N-dimethylaminoacetophenone, and the like. Examples of commercially available products include Irgacure 907, Irgacure 369 and Irgacure 379 manufactured by BASF Japan.

Specifically as said acyl phosphine oxide type photoinitiator, 2,4,6- trimethyl benzoyl diphenyl phosphine oxide, bis (2,4, 6- trimethyl benzoyl)-phenylphosphine oxide, bis (2, 6-, Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like. As a commercial item, Lucirin TPO by BASF Corporation, Irgacure 819 by BASF Japan Corporation, etc. are mentioned.

It is preferable that the compounding quantity of these (alpha)-amino acetophenone type photoinitiators and an acyl phosphine oxide type photoinitiators is 0.5 to 15 weight% of the total amount of a composition. If it is less than 0.5 weight%, the photocurability on copper is similarly lacking, and a coating film peels, and coating-film characteristics, such as chemical-resistance, fall. On the other hand, when it exceeds 15 weight%, the effect of reducing outgas is not acquired, and light absorption in the coating film surface becomes severe, and there exists a tendency for deep-curing property to fall.

In addition, as a photoinitiator, a photoinitiator, and a sensitizer which can be used suitably for the photocurable resin composition of this invention, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, 3 And higher amine compounds and xanthone compounds.

Specifically as said benzoin compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. are mentioned, for example.

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

Specifically as said anthraquinone compound, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t- butyl anthraquinone, 1-chloro anthraquinone, etc. are mentioned, for example.

Specifically as said thioxanthone compound, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, 2, 4- diisopropyl thioxanthone, etc. Can be mentioned.

Specifically as said ketal compound, acetophenone dimethyl ketal, benzyl dimethyl ketal, etc. are mentioned, for example.

Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4'-methyldiphenyl sulfide, 4-benzoyl-4'-ethyldiphenyl sulfide, 4 -Benzoyl-4'-propyldiphenyl sulfide, etc. are mentioned.

Specifically as said tertiary amine compound, For example, an ethanolamine compound and the compound which has a dialkylaminobenzene structure, For example, in a commercial item, 4,4'- dimethylamino benzophenone (Nippon Soda Co., Ltd. Nissocure MABP) ), 4,4'-diethylaminobenzophenone (EAB of Hodogaya Chemical Co., Ltd.), dialkylamino benzophenone, 7- (diethylamino) -4-methyl-2H-1-benzopyran- Dialkylamino group-containing coumarin compounds such as 2-one (7- (diethylamino) -4-methylcoumarin), ethyl 4-dimethylaminobenzoate (Kayacure (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.), 2 Ethyl dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics Co., Ltd.), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics Co., Ltd.), p-dimethylamino Isoamyl ethyl benzoate (Gayacure DMBI by Nippon Kayaku Co., Ltd.), 4-dimethylaminobenzo And the like can be mentioned 2-ethylhexyl (Van Dyke (solrol (Esolol) 507 to Van Dyk) Co., Ltd.), 4,4'-diethylamino-benzophenone (Hodogaya Chemical Co., Ltd. Preparation EAB).

Among the above-described photopolymerization initiators, photoinitiation aids and sensitizers, thioxanthone compounds and tertiary amine compounds are preferable. In particular, it is preferable to contain a thioxanthone compound from the point of deep-hardening property. Among them, it is preferable to include thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone .

As a compounding quantity of such a thioxanthone compound, it is preferable that it is 15 weight% or less of the whole composition. When the compounding quantity of a thioxanthone compound exceeds 15 weight%, thick film sclerosis | hardenability will fall and it will lead to a cost increase of a product. More preferably, it is 10 weight% or less.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable. Among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, Particularly preferred.

As said dialkylamino benzophenone compound, 4,4'- diethylamino benzophenone is preferable because of low toxicity. Since the dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm in the ultraviolet region, it is less colored, and provides a colored solder resist film reflecting the color of the colored pigment itself using a color pigment as well as a colorless transparent photosensitive composition. It becomes possible. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable at the point which shows the outstanding sensitizing effect with respect to the laser beam of wavelength 400-410 nm.

As a compounding quantity of such a tertiary amine compound, it is preferable to set it as 0.1-15 weight% of the whole composition. When the compounding quantity of a tertiary amine compound is less than 0.1 weight%, there exists a tendency for sufficient sensitization effect to not be acquired. When it exceeds 15 weight%, the light absorption in the surface of the dry solder resist coating film by a tertiary amine compound will become severe, and there exists a tendency for deep-curing property to fall.

As other photoinitiators, Irgacure 389 by the BASF Japan company, Irgacure 784, etc. can also be used preferably.

These photoinitiators, photoinitiation aids, and sensitizers can be used alone or as a mixture of two or more thereof.

It is preferable that the total amount of such a photoinitiator, a photoinitiator, and a sensitizer is 35 mass parts or less with respect to 100 mass parts of poly (meth) acrylates. When it exceeds 35 mass parts, there exists a tendency for deep-part sclerosis | hardenability to fall by these light absorption.

Moreover, since these photoinitiators, a photoinitiation adjuvant, and a sensitizer absorb a specific wavelength, in some cases, a sensitivity becomes low and may function as a ultraviolet absorber. However, they are not used for the purpose of improving the sensitivity of the composition. If necessary, light of a specific wavelength can be absorbed to increase the light reactivity of the surface, and the line shape and opening of the resist can be changed into vertical, tapered, and inverse tapered shapes, and the processing accuracy of the line width and aperture diameter can be improved. .

In order to improve a sensitivity, well-known conventional Nphenyl glycine, phenoxy acetic acid, thiophenoxy acetic acid, mercaptothiazole, etc. can be added to the photocurable resin composition of this invention as a chain transfer agent. Specific examples of the chain transfer agent include chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; Chain transfer agents having a hydroxyl group such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropane diol, mercaptobutanediol, hydroxybenzene thiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (ethylene dioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecylmercaptan , Propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanethiol, cyclohexanethiol, thioglycerol, 4,4-thiobisbenzenethiol, and the like.

Moreover, as a heterocyclic compound which has a mercapto group which functions as a chain transfer agent, for example, mercapto-4-butyrolactone (alias 2-mercapto-4-butanolide), 2-mercapto-4-methyl- 4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butylothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2 Mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto- 4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl-2-mercapto-4-butyrolactam, 2- Mercapto-5-valerolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto-5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam and 2-mercapto-6-hexa Nolactam, etc. are mentioned.

Especially as a heterocyclic compound which has a mercapto group which is a chain transfer agent which does not impair developability of a photocurable resin composition, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, Preference is given to 5-methyl-1,3,4-thiadiazole-2-thiol and 1-phenyl-5-mercapto-1H-tetrazole. These chain transfer agents may be used alone or in combination of two or more.

Moreover, the photocurable resin composition of this invention can also add the well-known carboxyl group-containing photosensitive resin conventionally used for the purpose of improving photosensitivity, developability, heat resistance, and an electrical property. The weight average molecular weight of the carboxyl group-containing photosensitive resin to be used varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is less than 2,000, the tack-free performance of the coating film may be inferior, the moisture resistance of the coating film after exposure is poor, the film may be reduced at the time of development, and the resolution may be greatly decreased. On the other hand, when a weight average molecular weight exceeds 150,000, developability may become remarkably bad and storage stability may be inferior.

The compounding quantity of such carboxyl group-containing photosensitive resin is 50 weight% or less of the composition whole quantity, Preferably the range of 10-40 weight% is suitable.

All these conventionally well-known thing can be used for these carboxyl group-containing photosensitive resin, and even if it is one type, it can use even if it mixes 2 or more types.

The thermosetting component can be used for the photocurable resin composition of this invention in order to provide heat resistance. Examples of the thermosetting component used in the present invention include amine resins such as melamine resins and benzoguanamine resins, block isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives and bismaleis. Known and commonly used thermosetting resins, such as a mead, an oxazine compound, an oxazoline compound, and a carbodiimide compound, can be used. Especially preferable are the thermosetting components which have a some cyclic ether group and / or cyclic thioether group (henceforth "cyclic (thio) ether group") in a molecule | numerator.

The thermosetting component which has a some cyclic (thio) ether group in such a molecule | numerator is a compound which has two or more types of groups of 3, 4 or 5 membered cyclic ether group or cyclic thioether group in a molecule | numerator, for example, a molecule | numerator Compound having a plurality of epoxy groups in the compound, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, namely episulfide resin Can be.

Examples of the polyfunctional epoxy compound include epoxidized vegetable oils such as adecaizer O-130P, adecaser O-180A, adecaser D-32, and adecaser D-55; JER (registered trademark) 828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, EHPE3150 manufactured by Daicel Chemical Industries, Ltd., Epiclone (registered trademark) 840 manufactured by DIC Corporation, Epiclone 850, Epiclone 1050, Epiclone 2055, Efototo (registered trademark) YD-011, YD-013, YD-127, YD-128, DER317, DER331, DER661, DER664, BASF made by Shinnitetsu Chemical Co., Ltd. Araldite 6071, Araldite 6084, Araldite GY250, Araldite GY260, Sumitomo Eg-01, ESA-014, ELA-115, ELA-128, Asahiga of Japan Bisphenol-A epoxy resins, such as AER330, AER331, AER661, and AER664, manufactured by Seigogyo Co., Ltd .; JERYL903 manufactured by Mitsubishi Chemical Corporation, Epiclone 152 manufactured by DIC Corporation, Epiclone 165, Efototo YDB-400, YDB-500 manufactured by Shinnitetsu Chemical Co., Ltd., DER542 manufactured by Dow Chemical, manufactured by BASF Japan Brominated epoxy resins such as Araldite 8011, Sumitomogagaku Kogyo Co., Ltd. Sumi-Epoxy ESB-400, ESB-700, and Asahi Kasei Kogyo AER711, AER714 (both trade names); JER152, jER154 made by Mitsubishi Chemical Co., Ltd., DEN431, DEN438 made by Dow Chemical Company, epiclon N-730, epiclon N-770 made by DIC company, epiclon N-865, made by Shinnitetsu Chemical Co., Ltd. Efototo YDCN-701, YDCN-704, Araldite ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307 by BASF Japan, EPPN-201, EOCN-1025 by Nippon Kayaku Co., EOCN -1020, EOCN-104S, RE-306, NC-3000, Sumi-Epoxy ESCN-195X, ESCN-220, Asahi Kasei Co., Ltd. make AERECN-235, ECN-299, etc. (all Novolak type epoxy resins; Epiclon 830 manufactured by DIC Corporation, jER807 manufactured by Mitsubishi Chemical Corporation, Efototo YDF-170, YDF-175, YDF-2004 manufactured by Shinnitetsu Chemical Co., Ltd., Araldite XPY 306 manufactured by BASF Japan Corporation, etc. (all Bisphenol F type epoxy resin of the brand name); Hydrogenated bisphenol A epoxy resins, such as Efototo ST-2004, ST-2007, ST-3000 (brand name) by Shin-Nitetsu Chemical Co., Ltd .; JER604 manufactured by Mitsubishi Chemical Corporation, Efototo YH-434 manufactured by Shinnitetsu Chemical Corporation, Araldite MY720 manufactured by BASF Japan Corporation, Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (all brand names) Glycidyl amine epoxy resins; Hydantoin type epoxy resins, such as Araldite CY-350 (brand name) by BASF Japan company; Alicyclic epoxy resins such as Celoxide (registered trademark) 2021 manufactured by Daicel Chemical Industries, Ltd., Araldite CY175 manufactured by BASF Japan Co., Ltd. (CY179, etc.); A trihydroxyphenylmethane type epoxy resin such as YL-933 manufactured by Mitsubishi Chemical Corporation, T.E.N., EPPN-501, and EPPN-502 manufactured by Dow Chemical Co. (all trade names); Biscylenol-type or biphenol-type epoxy resins such as YL-6056, YX-4000 and YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation; Bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Adeka Co., and EXA-1514 (trade name) manufactured by DIC Corporation; A bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; Tetraphenylolethane type epoxy resins such as jERYL-931 manufactured by Mitsubishi Chemical Co., Ltd. and Araldite 163 manufactured by BASF Japan Corporation; Heterocyclic epoxy resins such as Araldite PT810 manufactured by BASF Japan Co., Ltd. and TEPIC manufactured by Nissan Chemical Industries, Ltd. (both trade names); Diglycidyl phthalate resins such as Bremmer (registered trademark) DGT manufactured by Nippon Yushi Corporation; Tetraglycidyl xylenoylethane resins such as ZX-1063 manufactured by Shinnitetsu Chemical Co., Ltd .; Naphthalene-group containing epoxy resins, such as Shinnitetsu Chemical Co., Ltd. ESN-190, ESN-360, and DIC Corporation HP-4032, EXA-4750, EXA-4700; Epoxy resins having a dicyclopentadiene skeleton, such as HP-7200 and HP-7200H manufactured by DIC Corporation; Glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M manufactured by Nippon Yushi Co., Ltd .; A copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy modified polybutadiene rubber derivatives (for example, Daicel Chemical Co., Ltd. PB-3600, etc.), CTBN modified epoxy resins (for example, Shinnitetsu Chemical Co., Ltd. YR-102, YR-450, etc.) etc. are mentioned. However, it is not limited to these. These epoxy resins may be used alone or in combination of two or more. Among these, epoxide modified compounds by the peracetic acid method, such as EHPE3150, PB-3600, and Celoxide 2021 (all manufactured by Daicel Chemical Co., Ltd.), are preferred because they do not contain halogen ions as impurities. In addition, since epoxidized vegetable oils, such as adecaizer D-32, adecaser D-55, adecaser O-130P, and adecaser O-180A (all are manufactured by Adeka Co., Ltd.), do not contain a halogen similarly. desirable.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [( 3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methylacrylic Latex, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or these In addition to polyfunctional oxetanes such as oligomers or copolymers, oxetane alcohols and novolac resins, poly (p-hydroxystyrenes), cardo-type bisphenols, calix arenes, calyx resorcinrenes or silses Ether ether of resin which has hydroxyl groups, such as quoxane, etc. are mentioned. Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

As a compound which has a some cyclic thioether group in the said molecule | numerator, bisphenol-A episulfide resin YL7000 by Mitsubishi Chemical Corporation, etc. are mentioned, for example. Moreover, the 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.

As for the compounding quantity of the thermosetting component which has a some cyclic (thio) ether group in the said molecule, the range which becomes like this. Preferably it is 0.6-2.5 equivalent, More preferably, it is 0.8-2.0 equivalent with respect to 1 equivalent of carboxyl groups in a composition. When the compounding quantity of the thermosetting component which has several cyclic (thio) ether group in a molecule | numerator is less than 0.6, since a carboxyl group remains in a soldering resist film, heat resistance, alkali resistance, electrical insulation, etc. fall, it is unpreferable. On the other hand, when it exceeds 2.5 equivalent, since the low molecular weight cyclic (thio) ether group remains in a dry coating film, since the intensity | strength of a coating film etc. fall, it is unpreferable.

Moreover, the compound which has several isocyanate group or blocked isocyanate group can be added in 1 molecule as another thermosetting component. Examples of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule include a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound or a compound having a plurality of blocked isocyanate groups in one molecule, that is, a block isocyanate compound. .

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 -Xylylene diisocyanate and 2,4-tolylene dimer are mentioned. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Moreover, the adduct body, biuret body, and isocyanurate body of the isocyanate compound mentioned earlier are mentioned.

The blocked isocyanate group contained in the block isocyanate compound is a group in which an isocyanate group is protected by a reaction with a blocking agent and is temporarily inactivated. When heated to a predetermined temperature, the blocking agent dissociates to form an isocyanate group.

As such a block isocyanate compound, the addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound capable of reacting with the block agent include isocyanurate type, buret type, and adduct type. As the isocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate include the compounds as exemplified above.

As said isocyanate blocking agent, For example, phenol type blocking agents, such as a phenol, cresol, xylenol, chlorophenol, and ethylphenol; lactam-based blocking agents such as? -caprolactam,? -valerolactam,? -butyrolactam and? -propiolactam; Active methylene blockers such as ethyl acetoacetate and acetylacetone; But are not limited to, 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, Alcohol-based blocking agents such as butyl acetate, diacetone alcohol, methyl lactate and ethyl lactate; Oxime-based blocking agents such as formaldehyde scavengers, acetal aldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol and ethyl thiophenol; Acid amide block agents such as acetic amide and benzamide; Imide block agents such as succinic acid imide and maleic acid imide; Amine-based blocking agents such as xylidine, aniline, butylamine, and dibutylamine; Imidazole-based blocking agents such as imidazole and 2-ethylimidazole; Imine blockers such as methylene imine and propylene imine, and the like.

The said block isocyanate compound may be commercially available, for example, Sumidur (registered trademark) BL-3175, BL-4165, BL-1100, BL-1265, Desmodur (registered trademark) TPLS-2957, TPLS-2062 , TPLS-2078, TPLS-2117, Death Motum 2170, Death Motum 2265 (above, Sumitomo Bayurethane Co., Ltd. brand name), Coronate (registered trademark) 2512, Coronate 2513, Coronate 2520 (or more, Japan Polyurethane high Teacher production, brand name), B-830, B-815, B-846, B-870, B-874, B-882 (manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (Asahi Kasei Chemicals make, brand name) etc. are mentioned. Further, SMILDIR BL-3175 and BL-4265 are obtained by using methyl ethyl oxime as a block agent.

The compound which has a some isocyanate group or a blocked isocyanate group in said 1 molecule can be used individually by 1 type or in combination of 2 or more types.

As for the compounding quantity of the compound which has a some isocyanate group or a blocked isocyanate group in such one molecule, the ratio of 1-50 weight%, More preferably, 2-40 weight% of the whole composition is suitable. When the said compounding quantity is less than 1 weight%, the toughness of sufficient coating film is not obtained and it is unpreferable. On the other hand, when it exceeds 50 weight%, storage stability falls and it is unpreferable.

Moreover, a melamine derivative, a benzoguanamine derivative, etc. are mentioned as another thermosetting component. For example, methylolmelamine compounds, methylolbenzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. In addition, the alkoxy methylated melamine compound, the alkoxy methylated benzoguanamine compound, the alkoxy methylated glycoluril compound and the alkoxy methylated urea compound are the respective methylol melamine compounds, the methylol benzoguanamine compounds, the methylol glycoluril compounds and the methylol urea compounds. It is obtained by converting a methylol group into an alkoxy methyl group. It does not specifically limit about the kind of this alkoxy methyl group, For example, it can be set as a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, butoxymethyl group. Particularly, a melamine derivative having a formalin concentration of 0.2% or less is desirable for human body and environment.

As these commercial items, Cymel (registered trademark) 300, east 301, east 303, east 370, east 325, east 327, east 701, east 266, east 267, east 238, east 1141, east 272, east 202 , Copper 1156, copper 1158, copper 1123, copper 1170, copper 1174, copper UFR65, copper 300 (above, Mitsui Cyanamid Co., Ltd.), Nikalac (registered trademark) Mx-750, copper Mx-032, copper Mx-270, Mx-280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, the copper Mw-100LM, the copper Mw-750LM (above, Sanwa Chemical Co., Ltd.), etc. are mentioned. The thermosetting components may be used alone or in combination of two or more.

When a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is used, 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, Imidazole derivatives such as imidazole, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. Moreover, as what is marketed, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are brand names of an imidazole type compound) by Shikoku Chemical Co., Ltd., U-CAT (all registered) Trademark) 3503N, U-CAT3502T (all are brand names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all bicyclic amidine compounds and salts thereof) and the like. It does not specifically limit to these, What is necessary is just to accelerate the reaction of the thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group and / or an oxetanyl group, and a carboxyl group, and can also be used individually or in mixture of 2 or more types. Further, it is also possible to use at least one selected from the group consisting of guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid Or an S-triazine derivative such as an adduct may be used. Preferably, a compound that also functions as such an adhesion-imparting agent is used in combination with the above-mentioned thermosetting catalyst.

The compounding quantity of these thermosetting catalysts is sufficient in a normal quantity ratio, For example, Preferably it is 0.1-20 mass parts, More preferably, with respect to 100 mass parts of thermosetting components which have several cyclic (thio) ether group in a molecule | numerator. 0.5-15.0 mass parts.

The photocurable resin composition of this invention can mix | blend a coloring agent. As a coloring agent, conventionally well-known coloring agents, such as red, blue, green, and sulfur, can be used, and any of a pigment, dye, and a pigment may be used. However, from the viewpoint of the environmental load reduction and the effect on the human body, it is preferable that no halogen is contained.

Red colorant:

Examples of the red colorant include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridone, and the like. The same color index (CI; issued by The Society of Dyers and Colourists) number is attached.

Monoazo system: 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 system: Pigment Red 37, 38, 41.

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 pigments: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.

Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224, Pigment Red 174, Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, .

Diketopyrrolopyrrole-based pigments: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, 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.

Quinacridone pigments: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:

Examples of the blue colorant include phthalocyanine and anthraquinone, and pigments include compounds classified into pigments, specifically the following: pigment blue 15, pigment blue 15: 1, pig Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60.

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. may be used. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:

Examples of the green colorant include phthalocyanine series, anthraquinone series, and perylene series, and specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like can be used. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:

Examples of the yellow colorant include a monoazo system, a disazo system, a condensed azo system, a benzimidazolone system, an isoindolinone system, and an anthraquinone system, and specific examples include the following.

Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

Isoindolinone pigments: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

Benzimidazolone pigments: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.

Monoazo system: 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 system: 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, coloring agents such as violet, orange, brown, and black may be added.

Specific examples include pigment violet 19, 23, 29, 32, 36, 38, 42, solvent violet 13, 36, C.I. Pigment Orange 1, C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 16, C.I. Pigment Orange 17, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 43, C.I. Pigment Orange 46, C.I. Pigment Orange 49, C.I. Pigment Orange 51, C.I. Pigment Orange 61, C.I. Pigment Orange 63, C.I. Pigment Orange 64, C.I. Pigment Orange 71, C.I. Pigment orange 73, C.I. pigment brown 23, C.I. pigment brown 25, C.I. pigment black 1, C.I. pigment black 7 and the like.

Although the mixing | blending ratio of a coloring agent as mentioned above does not have a restriction | limiting in particular, 5 weight% or less in solid content of a composition is more preferable in 0.1 to 3 weight%.

In order to raise the physical strength of the coating film, etc. of the photocurable resin composition of this invention, a filler can be mix | blended as needed. As such a filler, well-known conventional inorganic or organic filler can be used, Especially barium sulfate, spherical silica, and talc are used preferably. In addition, metal hydroxides such as titanium oxide, metal oxides and aluminum hydroxides can also be used as extender pigment fillers in order to obtain white appearance and flame retardancy. The blending amount of the filler is preferably 75% by weight or less, more preferably 0.1 to 60% by weight of the total amount of the composition. When the compounding quantity of a filler exceeds 75 weight% of the whole composition, since the viscosity of an insulating composition becomes high, application | coating and moldability fall, or hardened | cured material becomes weak, it is unpreferable.

Moreover, the organic solvent can be used for the photocurable resin composition of this invention for the synthesis | combination of resin used for this invention, for manufacture of a composition, or for viscosity adjustment for apply | coating to a board | substrate or a carrier film.

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; Methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether And the like; Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate and methyl 2-hydroxyisobutyrate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum ether such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. These organic solvents are used alone or as a mixture of two or more kinds.

The photocurable resin composition of this invention is a well-known conventional thickening agent, such as a well-known thermal polymerization inhibitor, fine-grained silica, organic bentonite, and montmorillonite, an antifoamer, and / or a leveling agent, such as a silicone type, a fluorine type, and a polymer type, imidazole type as needed. Known additives such as silane coupling agents such as, thiazole series, triazole series, antioxidants, and rust inhibitors can be further blended.

The photocurable resin composition of this invention is adjusted to the viscosity suitable for the application | coating method with the said organic solvent, for example, and it is immersion coating method, flow coating method, roll coating method, bar coater method, screen printing method, curtain coating method on a base material. It is apply | coated by the method of these etc., and a tack free coating film can be formed by volatilizing (temporarily drying) the organic solvent contained in a composition at the temperature of about 60-100 degreeC. Moreover, the resin insulating layer can be formed by apply | coating the said composition on a carrier film, drying, and bonding what wound up as a film on a base material. Thereafter, through a photomask in which a pattern is formed by a contact type (or non-contact method), the pattern is selectively exposed by an active energy ray or directly by a laser direct exposure machine, and the unexposed portion is diluted with an aqueous alkali solution (for example, 0.3). To 3% by weight aqueous solution of sodium carbonate) to form a resist pattern. In the case of a composition containing a thermosetting component, for example, the carboxyl group of the carboxyl group-containing resin or the carboxyl group-containing photosensitive resin by heating to a temperature of about 140 to 180 ° C. and a plurality of cyclic ether groups in a molecule thereof. And / or a thermosetting component having a cyclic thioether group reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, hygroscopicity, adhesiveness, and electrical properties. Moreover, even when it does not contain a thermosetting component, by heat-processing, the ethylenically unsaturated bond of the photocurable component which remained in the unreacted state at the time of exposure thermally polymerizes, and a coating film characteristic improves, and it heats according to a purpose and a use Treatment (heat curing) can also be carried out.

Examples of the substrate include paper-phenolic resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / nonwoven fabric-epoxy resin, glass cloth / paper-epoxy resin, in addition to a printed wiring board or a flexible printed wiring board formed in advance. Copper clad laminates, polyimide films, PET films, glass substrates, ceramic substrates, wafer boards of all grades (FR-4, etc.) using composite materials such as synthetic fibers-epoxy resins, fluororesins, polyethylene, PPO, and cyanate esters It is available.

Volatilization drying after applying the photocurable resin composition of this invention is hot air circulation type drying, IR, hotplate, a convection oven, etc. (The hot air in a dryer is used, using what provided the heat source of the air heating system by steam. And a method of spraying the support from the nozzle).

After apply | coating the photocurable resin composition of this invention and volatilizing as follows, exposure (irradiation of an active energy ray) is performed with respect to the obtained coating film. An exposed part (part irradiated with an active energy ray) hardens | cures a coating film.

As an exposure machine used for the said active energy ray irradiation, a direct drawing apparatus (for example, the laser direct imaging apparatus which draws an image with a laser directly by CAD data from a computer), the exposure machine equipped with the metal halide lamp, the (super) high pressure mercury lamp A direct drawing device using an ultraviolet light lamp such as an exposure machine equipped with an optical device, an exposure machine equipped with a mercury short arc lamp, or a (ultra) high pressure mercury lamp can be used. As an active energy ray, any of a gas laser and a solid laser may be sufficient as long as the laser beam in the range whose maximum wavelength is 350-410 nm is used. Moreover, although the exposure amount changes with film thickness etc., it can generally be in the range of 5-800 mJ / cm <2>, Preferably it is 5-500 mJ / cm <2>. As the direct drawing apparatus, for example, those manufactured by Nippon Orbo Tech Co., Ltd. and Pantax Co., Ltd. may be used, and any apparatus may be used as long as it is an apparatus for oscillating laser light having a maximum wavelength of 350 to 410 nm.

As the developing method, a dipping method, a shower method, a spray method, a brush method, or the like can be used. As the developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, have.

The photocurable resin composition of this invention can also be used in the form of the dry film which has a soldering resist layer formed by apply | coating and drying a soldering resist to films, such as polyethylene terephthalate, in addition to the method of apply | coating directly to a base material in liquid form. The case of using the curable resin composition of the present invention as a dry film will be described below.

The dry film has a structure in which a carrier film, a solder resist layer, and a peelable cover film used as necessary are laminated in this order. The solder resist layer is formed by uniformly applying an alkali developable photocurable resin composition to a carrier film or cover film with a blade coater, a lip coater, a coater coater, a film coater, etc. in a thickness of about 10 to 150 μm, and drying it. After forming a soldering resist layer in a carrier film, a cover film is laminated | stacked on it, or a soldering resist layer is formed in a cover film, and this laminated body is laminated | stacked on a carrier film, and a dry film is obtained.

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

As a cover film, although a polyethylene film, a polypropylene film, etc. can be used, it is good that adhesive force with a soldering resist layer is smaller than a carrier film.

In order to produce a protective film (permanent protective film) on a printed wiring board using a dry film, the cover film is peeled off, the solder resist layer and the circuit-formed substrate are superimposed and bonded using a laminator or the like, and the solder resist layer is formed on the circuit-formed substrate. To form. When it exposes, develops, and heat-cures to the formed soldering resist layer as mentioned above, a cured coating film can be formed. The carrier film may be peeled off at any time before or after exposure.

<Examples>

Although an Example and a comparative example are shown to the following and this invention is concretely demonstrated to it, of course, this invention is not limited to the following Example. In addition, below "part" and "%" are mass references | standards unless there is particular notice.

(B-1) Carboxylic Acid Resin Synthesis Example 1

384 parts of PET flakes (manufactured by Mitsubishi Chemical Co., Ltd .: Nova Bex, IV value 1.1) were charged into a 1000-millimeter four-neck round bottom detachable flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. After that, it was immersed in the salt bath heated to 300 degreeC. Stirring was started when the PET was dissolved, and 1.6 parts of dibutyltin oxide was added. Subsequently, 134 parts of trimethylolpropane, which was previously heated to 130 ° C and dissolved, were added in small portions, taking care not to solidify the PET. In the meantime, the stirring speed was raised to 150 rpm in the stage where the viscosity fell. Next, it exchanged with the oil bath previously heated up to 240 degreeC from the salt bath, and kept the flask internal temperature at 220 degreeC +/- 10 degreeC, and made it react for 5 hours. Next, 518 parts of this reactant was poured into a 1000 mL four-necked flask equipped with a stirrer, an air inlet tube, a dividing tube, and a cooling tube. 81 parts of acrylic acid, 2.4 parts of paratoluenesulfonic acid, 0.8 parts of paramethoxyphenol, and methyl isobutyl After adding 212 parts of ketones and 112 parts of toluene, stirring and dissolving it uniformly, it immersed in the oil bath heated to 115 degreeC +/- 5 degreeC, and reaction was continued for predetermined time. After completion | finish of reaction, the acid value of the reaction liquid was measured, the acid equivalent aqueous alkali solution was added to the flask, it stirred, and it neutralized. Then, brine (20% by weight) was added and stirred. Thereafter, the solution was transferred to a separatory funnel, and the reaction solution and the same amount of methyl ethyl ketone were added to discard the aqueous phase. The oil phase was washed twice with brine (5% by weight) and the aqueous phase was discarded. In addition, the oil phase was washed twice with a small amount of tap water, and the aqueous phase was discarded. Next, the reaction solution was transferred to a beaker, the oil phase was stirred with hexane in the beaker, and the supernatant was discarded after standing. Finally, it concentrated by the evaporator and obtained PET containing acrylate resin. Next, 50 parts of PET-containing acrylate resins and 27 parts of carbitol acetate were added to a 300 mL four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube, and the flask was placed in a nitrogen atmosphere. It was immersed in the oil bath heated up to +/- 5 degreeC. Next, the carbitol acetate solution, in which 0.8 parts of triphenylphosphine and 0.4 part of metoquinone were dissolved in 10 parts of carbitol acetate, was slowly added dropwise, while 20 parts of tetrahydrophthalic anhydride was added in four portions every 2.5 hours for 10 hours to react. The resin solution of carboxyl group-containing acrylate of 65%, solid content acid value 128 mgKOH / g, and chlorine concentration of 20 ppm or less was obtained. This resin solution is called B-1.

(B-2) Carboxylic Acid Resin Synthesis Example 2

In a 500 milliliter four-neck round bottom detachable flask equipped with a stirrer, a nitrogen inlet tube and a cooling tube, 62 parts of 1,3-propylene glycol, 7.8 parts of trimethylolpropane, 0.77 parts of dibutyltin oxide, 40.6 parts of isophthalic acid, and PET 64 parts of flakes (Mitsubishi Chemical Co., Ltd. make: Novabeck, IV value 1.1) were thrown in, and the inside of a flask was made into nitrogen atmosphere, and it immersed in the oil bath heated up at 130 degreeC. It heated up to 180 degreeC when the content melt | dissolved. Then, it heated up to 235 degreeC and continued reaction for 1 hour. At 1 hour, 128 parts of PET flakes (manufactured by Mitsubishi Chemical Co., Ltd .: Novabecs, IV value 1.1) and 81.3 parts of isophthalic acid were added sequentially, and the reaction was continued for 14 hours until it became a transparent liquid phase.

Next, the flask internal temperature was maintained at 200 ° C, stirring was started, and 96 parts of trimellitic acid were added to dissolve. Thereafter, the reaction was continued for 8 hours. Next, the flask was cooled to 110 ° C, 1.02 parts of triphenylphosphine, 0.51 part of metoquinone and 287.7 parts of carbitol acetate were added and stirred. After continuing stirring, 51 parts of glycidyl methacrylates were added and it was made to react for 6 hours. In this way, the varnish of the carboxyl group-containing photosensitive compound of 65% of solid content and 90 mgKOH / g of solid content is obtained. Hereinafter, this resin solution is called B-2.

(B-3) Carboxylic Acid Resin Synthesis Example 3

192 parts of PET flakes (manufactured by Mitsubishi Chemical Co., Ltd .: Nova Bex, IV value 1.1) were put into a 500-milliliter four-neck round bottom detachable flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. After that, it was immersed in the salt bath heated to 300 degreeC. Stirring was started when the PET was dissolved, and 1.6 parts of dibutyltin oxide was added. Subsequently, 134 parts of trimethylolpropane, which was previously heated to 130 ° C and dissolved, were added in small portions, taking care not to solidify the PET. In the meantime, the stirring speed was raised to 150 rpm in the stage where the viscosity fell. Next, it exchanged with the oil bath previously heated up to 240 degreeC from the salt bath, the flask internal temperature was kept at 220 degreeC +/- 10 degreeC, and it was made to react for 5 hours, and then cooled to room temperature. Next, 121.6 parts of tetrahydrophthalic anhydride (THPA) and 240 parts of carbitol acetate were thrown in, and the flask was made into nitrogen atmosphere, and it was immersed in the oil bath heated up to 125 +/- 5 degreeC. Stirring was started slowly and reaction was performed for 3 hours, and the carboxylic acid resin of 65% of non volatile matters, 103 mgKOH / g of solid dispersion, and 20 ppm or less of chlorine concentration was obtained. This resin solution is called B-3.

Carboxyl group-containing photosensitive resin synthesis example

Orthocresol novolak-type epoxy resin (DIC Corporation, EPICLON N-695, softening point 95 degreeC, epoxy equivalent 214, average functional group number 7.6) 1070 parts (glycidyl group number (600 parts of diethylene glycol monoethyl ether acetate) Aromatic ring total number): 5.0 mol), 360 parts of acrylic acid (5.0 mol), and 1.5 parts of hydroquinone were thrown in, and it heated and stirred at 100 degreeC, and melt | dissolved uniformly. Subsequently, 4.3 parts of triphenylphosphines were thrown in, and it heated at 110 degreeC, and after reaction for 2 hours, it heated up at 120 degreeC and performed reaction for 12 hours further. 415 parts of aromatic hydrocarbons (Solbetso 150) and 456.0 parts (3.0 mol) of tetrahydrophthalic anhydride were added to the obtained reaction liquid, reaction was performed at 110 degreeC for 4 hours, after cooling, solid content 65% and solid content acid value 89 mgKOH / g and a chlorine concentration 400 ppm resin solution were obtained. This resin solution is called R-1.

(C) Polyester acrylate synthesis example

Into a 500 milliliter four-neck round bottom detachable flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube, 192 parts of PET flakes (Mitsubishi Chemical Co., Ltd., Novabecs (trade name)) were put in a nitrogen atmosphere. Then, it was immersed in the salt bath heated up to 300 degreeC. At the time point when the PET flakes dissolved, stirring was started and 0.65 parts of dibutyltin oxide was added.

Subsequently, 134 parts of trimethylolpropane, which was previously heated to 130 ° C and dissolved, were added in small portions, taking care not to solidify the PET. In the meantime, the stirring speed was raised to 150 rpm in the stage where the viscosity fell. Next, it exchanged with the oil bath previously heated up to 240 degreeC from the salt bath, and kept the flask internal temperature at 220 degreeC +/- 10 degreeC, and made it react for 5 hours. The reactants were yellow transparent and soft dotted at room temperature.

37 parts of toluene and 74 parts of methyl isobutyl ketone were introduced and mixed into 100 parts of the obtained reactants. Next, 65 parts of acrylic acid, 1.94 parts of paratoluenesulfonic acid and 0.26 parts of paramethoxyphenol were added, and the mixture was reacted at 110 ° C for 100 hours, and cooled to room temperature. The acid value of the obtained reaction liquid was measured, the aqueous alkali solution of an acid equivalent was added to the flask, it stirred, and it neutralized. Then, 50 parts of saline was added and stirred.

Thereafter, the solution was transferred to a separatory funnel to discard the aqueous phase, and the oil phase was washed twice with 100 parts of 5% by weight NaCl solution. After washing, the solvent component was distilled off by an evaporator to obtain a reactant having a nonvolatile content of 100%. The reaction product obtained was a brown transparent soft liquid at room temperature. This resin solution is called C-1.

(D-1) Epoxy Resin Synthesis Example 1

192 parts of PET flakes (manufactured by Mitsubishi Chemical Co., Ltd .: Nova Bex, IV value 1.1) were put into a 500-milliliter four-neck round bottom detachable flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. After that, it was immersed in the salt bath heated to 300 degreeC. At the time when PET dissolved, stirring was started and 0.65 parts of dibutyltin oxide was added. Subsequently, 45 parts of trimethylolpropane, which was previously heated to 130 ° C and dissolved, were added in small portions, taking care not to solidify the PET. Meanwhile, the stirring speed was increased to 150 rpm while the viscosity decreased. Next, it exchanged with the oil bath previously heated up to 240 degreeC from the salt bath, and maintained inside temperature of the flask at 220 degreeC +/- 10 degreeC, made it react for 5 hours, and then cooled to room temperature. 200 parts of the depolymerized thus obtained were put into a 500 milliliter four-necked round-separable flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. The flask was heated to 145 ° C ± 5 ° C after the nitrogen atmosphere. It was immersed in an oil bath. About 30 minutes after starting stirring, 83 parts of tetrahydrophthalic anhydride was added, and stirring was continued. In this way, the carboxylic acid resin of acid value 112 mgKOH / g was obtained. Next, 40 parts of this carboxylic acid resin were put into a 500 milliliter four-necked round-separable flask equipped with a stirrer, a nitrogen inlet tube and a cooling tube, and further YD-825GS (manufactured by Shinnitetsu Chemical Co., Ltd., epoxy equivalent 185). 60 parts of g / eq. and chlorine concentration 160 ppm) were put, the inside of a flask was made into nitrogen atmosphere, the oil bath was heated up gradually, after the content melt | dissolved, the oil bath was heated up to 110 degreeC +/- 5 degreeC, and reaction was carried out. Subsequently, an epoxidized resin having an epoxy equivalent of 421 g / eq. And a chlorine concentration of 93 ppm was obtained. This is called epoxy resin D-1.

(D-2) Epoxy Resin Synthesis Example 2

192 parts of PET flakes (manufactured by Mitsubishi Chemical Co., Ltd .: Nova Bex, IV value 1.1) were put into a 500-milliliter four-neck round bottom detachable flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. After that, it was immersed in the salt bath heated to 300 degreeC. At the time when PET dissolved, stirring was started and 0.65 parts of dibutyltin oxide was added. Subsequently, 104 parts of neopentylglycols which were heated and dissolved at 130 ° C in advance were added little by little, taking care not to solidify the PET. In the meantime, the stirring speed was raised to 150 rpm in the stage where the viscosity fell. Next, it exchanged with the oil bath previously heated up at 240 degreeC from the salt bath, and after making reaction inside the flask hold | maintain at 220 degreeC +/- 10 degreeC for 5 hours, it cooled to room temperature. 118 parts of the depolymerized thus obtained were put into a 500 milliliter four-necked round-separable flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube, and the inside of the flask was placed in a nitrogen atmosphere, followed by 110 parts of o-hydroxybenzoic acid, 0.5 part of dibutyltin oxide was thrown in, and the flask was made into nitrogen atmosphere. The condensate was removed over about 4 to 6 hours while the hot water bath was gradually heated to 200 ° C, the oil bath was lowered when the acid value sufficiently decreased, and the flask contents were taken out to obtain a phenol resin. Next, 45.1 parts of this phenol resin was put into a 500 milliliter four-necked round-separable flask equipped with a stirrer, a nitrogen inlet tube and a cooling tube, and YD-825GS (manufactured by Shinnitetsu Chemical Co., Ltd., epoxy equivalent 185 g /). 66.3 parts of eq., chlorine concentration of 160 ppm) was added, the flask was placed in a nitrogen atmosphere, the oil bath was gradually heated up, and after the contents were dissolved, the oil bath was heated to 110 ° C ± 5 ° C to continue the reaction. And an epoxy equivalent of 447 g / eq. And an chlorine concentration of 95 ppm were obtained. This is called epoxy resin D-2.

Examples 1-14 and Comparative Examples 1-2

Using the resin of each said synthesis example, it mix | blended in the ratio (mass part) shown in Table 1 with the various components shown in following Table 1, pre-mixed with a stirrer, and knead | mixed with a triaxial roll mill, and the photosensitive resin for soldering resists The composition was prepared.

Performance evaluation:

<Polyester-derived Compound Content>

In the composition of the said Example and a comparative example, the content rate (in organic component) of the compound derived from the said General formula (1) is shown in Table 2.

<Optimum exposure dose>

After buffing-roll polishing a circuit pattern substrate having a copper thickness of 35 μm, washing with water and drying, the photosensitive resin compositions of the above examples and comparative examples were applied to the entire surface by screen printing, and then heated in a hot air circulating drying furnace at 80 ° C. It was dried for 60 minutes. After drying, exposure was performed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high pressure mercury lamp (short arc lamp), and developed (30 ° C., 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution). Was performed for 60 seconds, the optimum exposure amount was set when the pattern of the remaining step tablet was seven stages.

<Developability>

The photosensitive resin composition of the said Example and the comparative example was apply | coated so that the film thickness after drying might be about 25 micrometers by screen printing on the copper-clad board | substrate, and it dried for 30 minutes by 80 degreeC hot-air circulation type drying furnace. After drying, it subjected to development by a 1 wt% Na ₂ CO ₃ aqueous solution was measured by the time elapsed before the removal drying a coating film on the stopwatch.

<Touch-up Drying>

The photosensitive resin composition of the said Example and the comparative example was apply | coated whole surface by screen printing on the patterned copper foil board | substrate, respectively, it dried for 30 minutes by the 80 degreeC hot air circulation type drying furnace, and cooled to room temperature. The PET film was crimped | bonded to this board | substrate, and the adhesive state of the film at the time of peeling a negative film after that was evaluated. The criteria are as follows.

(Double-circle): When peeling a film, there is no resistance at all and a trace does not remain in a coating film.

(Circle): Although there is no resistance at all when peeling a film, a trace adheres to a coating film a little.

(Triangle | delta): When peeling a film, there exists a little resistance and a trace adheres to a coating film a little.

X: When peeling a film, there exists a resistance and a trace adheres to a coating film clearly.

<Resolution>

The circuit pattern board | substrate of 300/300 micrometers of line / space, and 35 micrometers of copper thicknesses is rinsed after buffing-rolling, washing and drying the photosensitive resin composition of an Example and a comparative example, and apply | coating by the screen printing method, and the hot air of 80 degreeC It was dried for 30 minutes by a circulation drying furnace. After drying, exposure was performed using an exposure apparatus equipped with a high pressure mercury lamp. The exposure pattern used the negative which draws the line of 20/30/40/50/60/70/80/90/100 micrometers in the space part. The exposure amount was irradiated with active energy rays so as to be the optimum exposure amount of the photosensitive resin composition. After exposure, the 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa, and a cured coating film was obtained by performing thermal curing at 150 ° C. for 60 minutes. The minimum residual line of the cured coating film of the obtained photosensitive resin composition for soldering resists was calculated | required using the optical microscope which adjusted 200 times, and made this resolution.

<Halogen content>

Using the resin solution obtained by each said synthesis example, it mix | blended in the ratio (mass part) shown in Table 1 with the various components shown in the said Table 1, pre-mixed with a stirrer, and knead | mixed with a triaxial roll mill and photosensitive resin The composition was prepared. Halogen ion impurity content (total of chlorine and bromine) was quantified by using the flask-burning-ion-ion chromatograph method based on the JPCA standard for the obtained photosensitive resin composition. When halogen ion concentration is 20 ppm or less (quantitative limit), a description is made "-". The results are shown in Table 2.

Characteristic test:

The composition of each said Example and the comparative example was apply | coated whole surface by the screen printing on the patterned copper foil board | substrate, dried at 80 degreeC for 30 minutes, and left to stand to room temperature. The substrate is exposed to a solder resist pattern at an optimum exposure dose using an exposure apparatus equipped with a high pressure mercury lamp (short arc lamp), and a phenomenon of 60 seconds under a spray pressure of 0.2 MPa is applied to a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. It carried out and obtained the resist pattern. This board | substrate was irradiated with ultraviolet-ray on the conditions of the integrated exposure amount 1000mJ / cm <2> with a UV conveyor, and it heated at 150 degreeC for 60 minutes, and hardened | cured. The properties of the obtained printed board (evaluation board) were evaluated as follows.

&Lt; Soldering heat resistance &

The evaluation board | substrate with which the rosin type flux was apply | coated was immersed in the solder tank set previously at 260 degreeC, and the flux was wash | cleaned with denatured alcohol, and the expansion and peeling of the resist layer by visual observation were evaluated. The criteria are as follows.

(Double-circle): Peeling is not confirmed even if it immerses 6 times or more for 10 second.

(Circle): Peeling is not confirmed even if immersion is repeated 3 times or more for 10 second.

(Triangle | delta): When it immerses 3 times or more for 10 second, it peels a little.

X: There exists expansion and peeling in a resist layer within 3 times of immersion for 10 second.

<Alkali resistance>

The evaluation board | substrate was immersed in 10 weight% NaOH aqueous solution for 30 minutes at room temperature, and the immersion, the elution of a coating film, and peeling by tape peeling were confirmed. The criteria are as follows.

(Circle): No infiltration, elution, peeling.

(Triangle | delta): A little soaking, elution, or peeling are confirmed.

X: Soaking, elution, or peeling are largely confirmed.

Peelability

The evaluation board | substrate was immersed in 10 weight% NaOH aqueous solution at 60 degreeC, and the soldering resist layer was evaluated whether it can peel from a board | substrate. The evaluation criteria are as follows.

(Double-circle): Peeling is possible by immersion for 15 minutes.

(Circle): Peeling is possible by immersion for 30 minutes.

(Triangle | delta): After 60 minutes immersion, a little residue is confirmed.

X: It is impossible to peel.

Electrode discoloration resistance

An evaluation substrate was fabricated under the above conditions using a comb electrode pattern of line / space = 50/50 μm instead of the copper foil substrate, and a bias voltage of 30 V DC was applied to the comb electrode under a humidified condition of 121 ° C. and 97% RH. Then, the discoloration degree of the coating film around the electrode after 100 hours was evaluated. The criteria are as follows.

(Circle): No discoloration of a coating film.

(Triangle | delta): The discoloration of a coating film is confirmed slightly.

X: There is discoloration of a coating film.

<Dry Film Production>

After properly diluting the photosensitive resin compositions for soldering resists of Example 1 and Comparative Example 1 with methyl ethyl ketone, respectively, the PET film (FB-50 manufactured by Toray: 16 μm was used so that the film thickness after drying was 30 μm using an applicator. ), And dried at 40 to 100 ° C to obtain a dry film.

<Substrate Fabrication>

After buffing the circuit-formed substrate, the dry film produced by the above method was subjected to a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.) at a pressure of 0.8 MPa, 70 ° C. for 1 minute, and a vacuum of 133.3 Pa. It heated and laminated on conditions, and obtained the board | substrate (unexposed board | substrate) which has an unexposed soldering resist layer. The obtained board | substrate was carried out similarly to the said evaluation method, and each test of the optimal exposure amount, developability, resolution, solder heat resistance, alkali resistance, peelability, and electrode discoloration tolerance was done.

The evaluation results are shown in Table 2.

As is clear from the results shown in Table 2, in Comparative Examples 1 and 2 using the photocurable resin composition containing no polyester-derived compounds (carboxylic acid resin, poly (meth) acrylate, and epoxy resin) of the present invention. It was not possible to peel a soldering resist layer from a board | substrate by the immersion process in 10 degreeC NaOH aqueous solution at 60 degreeC.

On the other hand, the photocurable resin composition of this invention of Examples 1-14 is compatible with general alkali resistance and peelability by aqueous alkali solution, and when used as a soldering resist, it is normally due to the defect resulting from a soldering resist formation process. It becomes possible to reuse a board | substrate by peeling and washing only a soldering resist cured film from the printed wiring board discarded on the back surface.

Claims (6)

(A) poly (meth) acrylate (except poly (meth) acrylate derived from a compound containing a structure represented by the following formula (1)),
All containing one or two or more of (B) carboxylic acid resin, (C) poly (meth) acrylate, and (D) epoxy resin, all derived from a compound containing a structure represented by the following formula (1): Photocurable resin composition for forming a cured film on the circuit of the printed wiring board characterized by the above-mentioned.
&Lt; Formula 1 >

(Wherein R ¹ represents a trivalent alcohol derivative, R ² represents CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , a substituted or unsubstituted aromatic ring, and R ³ is A substituted or unsubstituted aromatic ring, where l is an integer of 0 or less than 2, l + m is a number of 3, m is an integer of 1 or more and 3 or less, and n is an integer of 1 or more and less than 10) The method according to claim 1, wherein any one or two or more of the carboxylic acid resins (B), poly (meth) acrylates (C) and epoxy resins (D) are contained in a ratio of 20% by weight or more with respect to the organic material in the composition. It contains, The photocurable resin composition characterized by the above-mentioned. Any one or two or more of (B) carboxylic acid resins, (C) poly (meth) acrylates, and (D) epoxy resins, all derived from a compound containing a structure represented by the following formula (1) It is contained in the ratio of 20 weight% or more with respect to an organic substance, The photocurable resin composition for forming a cured film on the circuit of the printed wiring board.
&Lt; Formula 1 >

(Wherein R ¹ represents a trivalent alcohol derivative, R ² represents CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , a substituted or unsubstituted aromatic ring, and R ³ is A substituted or unsubstituted aromatic ring, where l is an integer of 0 or less than 2, l + m is a number of 3, m is an integer of 1 or more and 3 or less, and n is an integer of 1 or more and less than 10) The photocurable dry film obtained by apply | coating and drying the photocurable resin composition of any one of Claims 1-3 on a film. Hardened | cured material obtained by hardening | curing the photocurable dry film obtained by apply | coating and drying the photocurable resin composition or said photocurable resin composition of any one of Claims 1-3 on a film in a pattern form. After curing the photocurable dry film obtained by apply | coating and drying the photocurable resin composition or said photocurable resin composition of any one of Claims 1-3 on a film in pattern form, the cured film obtained by thermosetting Having printed wiring board.