JP5990232B2 - Photocurable resin composition, dry film and cured product thereof, and printed wiring board using them - Google Patents

Description

  The present invention is an alkali-developable photo-curable resin composition that can be peeled off with an aqueous alkali solution even when it is a solder resist cured film after ultraviolet curing and heat curing, and the substrate can be reused. The present invention relates to the dry film and the cured product and a printed wiring board using them.

  At the time of 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 the solder from adhering to a portion where the conductor circuit is not protected or soldered. As a method of forming a cured solder resist film, a method of forming a solder resist cured film by printing in a pattern by screen printing and curing by ultraviolet rays or heat, or after applying and drying a solder resist composition on the substrate surface There is a method of forming a cured solder resist by exposing, developing and heat-curing in a pattern.

In the process of forming a solder resist cured film as described above, defects often occur due to printing defects such as repellency and bleeding during printing, foreign matter contamination, pinholes, misalignment during exposure, etc. However, when the substrate is discarded due to a defect caused by such a solder resist formation process, it starts with the formation of the laminated plate, and all the processes up to that time, such as the formation of the conductor circuit, drilling, and hole filling, are wasted, This leads to a decrease in yield.
Therefore, a method of peeling the cured solder resist film and reusing the substrate has been proposed (see, for example, Patent Document 1).

In Patent Document 1, by using a mixed solution of sodium hydroxide or potassium hydroxide, a glycol ether having a chain length of 3 to 6 and water as a stripping solution, the solder resist cured by ultraviolet irradiation is stripped, It has been proposed that the substrate can be reused.
However, the peeling described in Patent Document 1 is effective only for a cured product cured by ultraviolet irradiation, and it is impossible to peel a cured product that has been heat-cured.

In addition, a peeling solution that peels even a cured solder resist film after being cured by ultraviolet irradiation or heat and enables reuse of the substrate has been proposed (see, for example, Patent Document 2).
However, in Patent Document 2, an alkali metal hydroxide and an aprotic polar solvent (N-methyl-2-pyrrolidone) are used as the stripping solution, and it cannot be said that the burden on the environment is small.

Japanese Patent Laid-Open No. 7-115048 (Claims) JP-A-11-145594 (Claims)

The present invention has been made in view of the prior art as described above, and it is an alkaline aqueous solution, for example, a 5-20 wt% sodium hydroxide aqueous solution at 60 ° C., even for a solder resist cured film after ultraviolet curing and thermal curing. It is intended to provide a photocurable resin composition and a dry film thereof that can be peeled off by treatment for about 10 to 60 minutes and can reuse the substrate.
In particular, by using a photo-curable resin composition containing a polyester-derived curable component as a main component as a solder resist, a photo-curable resin composition that can also recover polyester raw materials such as terephthalic acid from the waste liquid. And it aims at providing the dry film.
Furthermore, the objective of this invention is providing the printed wiring board which can peel a soldering resist cured film and can reuse a board | substrate by using such a photocurable resin composition and its dry film. is there.

（式中、Ｒ^１は（ｍ＋ｌ）価の多価アルコール誘導体を表し、Ｒ^２はＣＨ_２、Ｃ_２Ｈ_４、Ｃ_３Ｈ_６、Ｃ_４Ｈ_８、置換もしくは無置換の芳香族環のいずれかを表し、Ｒ^３は置換もしくは無置換の芳香族環を表し、ｍ及びｎは１以上、１０未満の整数であり、ｌは０もしくは１以上の整数である。） In order to achieve the above object, according to the present invention, even a cured film after UV curing and thermal curing can be performed in an alkaline aqueous solution, for example, 5 to 20 wt% sodium hydroxide aqueous solution at 60 ° C. for 10 to 60 minutes. A photocurable resin composition that can be peeled off by being treated to the extent is provided, and according to one embodiment thereof, all are derived from a compound containing a structure represented by the following general formula (1): B) One or two or more of carboxylic acid resin, (C) poly (meth) acrylate and (D) epoxy resin are contained at a ratio of 20 wt% or more with respect to the organic matter in the composition. A photocurable resin composition is provided.

(Wherein R ¹ represents an (m + 1) -valent polyhydric alcohol derivative, and R ² represents any of 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 integers of 1 or more and less than 10, and l is 0 or an integer of 1 or more.)

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

Further, according to the present invention, the photocurable resin composition obtained by applying and drying the photocurable resin composition on a film, the photocurable resin composition or the dry film is cured. A cured product obtained, particularly a cured product obtained by photocuring on copper, and a cured product obtained by photocuring in a pattern are also provided.
Furthermore, according to the present invention, there is also provided a printed wiring board characterized by having a cured film obtained by photocuring the photocurable resin composition or dry film in a pattern and then thermosetting.

The curable resin or compound used in the photocurable resin composition of the present invention is a carboxylic acid resin, poly (meth) acrylate or epoxy resin derived from a compound containing the structure represented by the general formula (1). Since the polyester is derived from polyester, the ester bond responsible for the main skeleton is hydrolyzed by treatment with an alkaline aqueous solution, and the carboxyl group and hydroxyl group generated by the hydrolysis express strong hydrophilicity. The inventors have found that the film can be peeled off by an alkaline aqueous solution. By utilizing this action as, for example, a solder resist composition, the main skeleton is not hydrolyzed because the curable resin or compound used in the conventional solder resist composition is a novolak type epoxy resin or a novolak type epoxy acrylate. The defect of poor peelability was overcome. Therefore, when a defect occurs in the solder resist cured film manufacturing process, the substrate can be reused by removing the solder resist from the substrate. Moreover, unlike the conventional epoxy acrylate modified resin, the raw material which does not contain a halogen ion can be used. Therefore, it can be made halogen-free, and a cured film excellent in electrical insulation, heat resistance, and dryness to touch can be formed.
Therefore, the photocurable resin composition of the present invention can be advantageously applied to the formation of a cured film such as a solder resist of a printed wiring board or a flexible printed wiring board.
Furthermore, since the photocurable resin composition of the present invention contains a curable component derived from polyester as a main component, it is also possible to collect a raw material of polyester such as terephthalic acid from the waste liquid of the peeled solder resist, It is extremely useful in terms of resource saving and environmental protection.

（式中、Ｒ^１は（ｍ＋ｌ）価の多価アルコール誘導体を表し、Ｒ^２はＣＨ_２、Ｃ_２Ｈ_４、Ｃ_３Ｈ_６、Ｃ_４Ｈ_８、置換もしくは無置換の芳香族環のいずれかを表し、Ｒ^３は置換もしくは無置換の芳香族環を表し、ｍ及びｎは１以上、１０未満の整数であり、ｌは０もしくは１以上の整数である。） As described above, the photocurable resin composition of one embodiment of the present invention is characterized by (A) poly (meth) acrylate (provided by the following general formula (1)) conventionally used as a photosensitive component. (B) a carboxylic acid resin, which is derived from a compound having a structure represented by the following general formula (1): (C) ) It is to contain any one or two or more of poly (meth) acrylate and (D) epoxy resin.

(Wherein R ¹ represents an (m + 1) -valent polyhydric alcohol derivative, and R ² represents any of 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 integers of 1 or more and less than 10, and l is 0 or an integer of 1 or more.)

  According to the studies by the present inventors, when such a photocurable resin composition is used as a solder resist, it is sufficient for general treatment such as immersion in 10 wt% NaOH at 25 ° C. for 30 minutes. It has been found that the cured solder resist coating film can be peeled off by treating with a 5-20 wt% NaOH aqueous solution at 60 ° C. for about 10 to 60 minutes while having excellent alkali resistance. It has come to be completed.

Further, according to the study by the present inventors, (B) carboxylic acid resin, (C) poly (meth) acrylate and (D), all derived from a compound containing the structure represented by the general formula (1). When the epoxy resin is 20 wt% or more based on the organic matter in the composition by any one kind or a combination of two or more kinds, (A) poly (meth) acrylate other than the above (the general formula (1) It has been found that the same effect can be obtained even if the poly (meth) acrylate) is not contained, or does not contain a compound represented by the general formula (1). However, (B) carboxylic acid resin, (C) poly (meth) acrylate and (D) epoxy resin derived from the compound containing the structure represented by the general formula (1) are any one or two kinds. It is preferable to blend so as to be 80 wt% or less with respect to the organic matter in the composition by the above combination. When blended in a large amount exceeding this ratio, the alkali resistance of the cured coating film may be lowered, which is not preferable. In addition, when other (A) poly (meth) acrylates other than poly (meth) acrylate derived from the compound containing the structure represented by the general formula (1) are contained, the optical characteristics such as sensitivity are improved. It is advantageous.
Hereinafter, each component of the photocurable resin composition of the present invention will be described in detail.

First, (A) poly (meth) acrylate used in the present invention is derived from a compound that does not include the structure represented by the general formula (1) or does not include the structure represented by the general formula (1). Any poly (meth) acrylate can be used and is not limited to a specific polyfunctional (meth) acrylate. Specific examples include, for example, polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or their ethylene oxide adduct, propylene oxide adduct, or ε-caprolactone addition. Polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate, and polyvalent acrylates such as ethylene oxide adduct or propylene oxide adduct of these phenols; glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol Polyvalent acrylates of glycidyl ethers such as propane triglycidyl ether and triglycidyl isocyanurate; Chromatography ether polyols, directly acrylated polycarbonate diols, polyols, such as hydroxyl terminated polybutadiene, or urethane acrylated acrylates and melamine acrylates, and / or the like each methacrylates corresponding to the acrylates via diisocyanates.
In the present specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

The (B) carboxylic acid resin derived from the compound having the structure represented by the general formula (1) used in the present invention is a polybasic acid as described later in the compound having the structure represented by the general formula (1). Or it is obtained by making the anhydride react. Preferably, (a) the polyester is (b) depolymerized with a polyol having two or more hydroxyl groups in one molecule, or at the same time after depolymerization, the (c) polybasic acid or anhydride thereof is used. It is obtained by reacting.
The (B) carboxylic acid resin may have a photosensitive group. In this case, if the compound having the structure represented by the general formula (1) is reacted with a compound having one or more ethylenically unsaturated groups in the molecule as described later and a polybasic acid or an anhydride thereof, Good. Preferably, (a) the polyester is (b) one or more ethylenes in the molecule at the same time or after depolymerization with (b) a polyol having two or more hydroxyl groups in one molecule. What is necessary is just to make the compound which has an ionic unsaturated group, and (c) polybasic acid or its anhydride react. The component (d) and the component (c) may be reacted together or sequentially. In the case of sequential reaction, the reaction order may be (d) component first, then (c) component, or (c) component first, then (d) component reacted. However, the reaction ratio must be such that one or more, preferably two or more carboxyl groups are generated.

  The (C) poly (meth) acrylate derived from the compound having the structure represented by the general formula (1) used in the present invention will be described later in the compound having the structure represented by the general formula (1). A compound having one or more ethylenically unsaturated groups in the molecule is reacted, or a polybasic acid or an anhydride thereof is reacted, and one or more ethylenically unsaturated groups are reacted in the molecule. It is obtained by reacting a compound having Preferably, (a) the polyester is (b) one or more ethylenes in the molecule at the same time or after depolymerization with (b) a polyol having two or more hydroxyl groups in one molecule. (C) a compound having one or more ethylenically unsaturated groups in the molecule thereof, or (c) a reaction with a polybasic acid or an anhydride thereof. Is obtained by reacting.

  The epoxy resin (D) derived from the compound having the structure represented by the general formula (1) used in the present invention is reacted with epichlorohydrin to the compound having the structure represented by the general formula (1), or After treatment with a polybasic acid or an anhydride thereof or a monocarboxylic acid having a phenol group, it is obtained by reacting epichlorohydrin or a compound having a plurality of epoxy groups in the molecule. Preferably, (a) polyester is (b) depolymerized with a polyol having two or more hydroxyl groups in one molecule, and the resulting depolymer is reacted with epichlorohydrin as it is, or (c) polybasic acid Alternatively, it can be obtained by treating with an anhydride thereof or (e) a monocarboxylic acid having a phenol group and then reacting epichlorohydrin or (f) a compound having a plurality of epoxy groups in the molecule.

  In the depolymerization of the polyester, the ratio of the polyester and the polyol having two or more hydroxyl groups in one molecule is the number of moles (α) of repeating units of the polyester and the polyol having two or more hydroxyl groups in one molecule. The ratio of the number of moles (β) is suitably (α) / (β) = 0.5-3, preferably in the range of 0.8-2. When the ratio is less than 0.5, the polyol component is excessively contained, the ratio of the aromatic ring derived from the polyester is decreased, and the effect of improving heat resistance and chemical resistance is decreased, which is not preferable. On the other hand, when the ratio is greater than 3, the depolymerized product is crystallized in most cases and is insoluble in the solvent, which is not preferable.

  The polyester (a) may be any conventionally known polyester, and examples thereof include polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and liquid crystal polymer. In addition, recycled PET and recycled PET recovered from waste such as PET bottle waste can be used, which are preferable from the viewpoint of environmental protection. The collected PET can be crushed and washed, and the recycled PET can be obtained from the market after being washed and pelletized. The shape of the polyester is not particularly limited, but is preferably in the form of pellets and / or flakes. Moreover, although it is not necessary to grind | pulverize finely in powder form, the grind | pulverized thing may be used.

  (B) As the polyol having two or more hydroxyl groups in one molecule, all of bifunctional polyols, trifunctional or higher polyols, etc. can be used, and they can be used alone or in combination of two or more. .

  Examples of the bifunctional polyol include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, 1,3-butanediol, Neopentyl glycol, spiro glycol, dioxane glycol, adamantanediol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2-methylpropanediol 1, Bifunctional phenols such as 3,3-methylpentanediol 1,5, hexamethylene glycol, octylene glycol, 9-nonanediol, 2,4-diethyl-1,5-pentanediol, bisphenol A Ethylene oxide modified compound of bisphenol A, propylene oxide modified compound of bifunctional phenol such as bisphenol A, ethylene oxide of bisphenol A, propylene oxide copolymer modified compound, copolymer polyether polyol of ethylene oxide and propylene oxide, polycarbonate diol, Adamantanediol, polyether diol, polyester diol, polycaprolactone diol (e.g., Plaxel 205, Plaxel L205AL, Plaxel 205U, Plaxel 208, Plaxel L208AL, Plaxel 210, Plaxel 210N, Plaxel 212, Plaxel L212AL, Plaxel 220, Plaxel 220N, Plaxel 220NP1, Plaxel L220AL, Plaque 230, Plaxel 240, Plaxel 220EB, Plaxel 220EC; all manufactured by Daicel Chemical Industries, Ltd .; trade name), hydroxyl group-terminated polyalkanediene diols (eg, 1,4-polyisoprenediol, 1,4- and 1,2-polybutadiene diols and elastomers such as hydrogenated products thereof. Examples of commercially available products of the above hydroxyl group-terminated polyalkanediene diols include EPOL (registered trademark; hydrogenated polyisoprene diol, molecular weight). 1,860, average polymerization degree 26, manufactured by Idemitsu Kosan Co., Ltd.), PIP (polyisoprene diol, molecular weight 2,200, average polymerization degree 34, manufactured by Idemitsu Kosan Co., Ltd.), polytail (registered trademark) H (hydrogenated) Polybutadiene diol, molecular weight 2,200, average degree of polymerization 39, 3 Ryo Chemical Co., Ltd.), R-45HT (polybutanediol, molecular weight 2,270, average polymerization degree 42, manufactured by Idemitsu Kosan Co., Ltd.), and the like.

  Examples of the tri- or higher functional polyol include glycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, adamantanetriol, polycaprolactone triol (for example, plaxel 303, plaxel 305, Plaxel 308, Plaxel 312, Plaxel L312AL, Plaxel 320ML, Plaxel L320AL; all of which are manufactured by Daicel Chemical Industries, Ltd .; trade names), and those having aromatic rings include ethylene oxides and propylene oxides of trifunctional or higher phenol compounds Sake manufactured by Shikoku Kasei Kogyo Co., Ltd. is exemplified as a modified product or a compound having a heterocyclic ring. In particular, when trimethylolpropane is used, an amorphous semi-solid fluid material that does not become turbid when obtained as a depolymerized product is obtained, and the solubility in a solvent is further increased.

  As said (c) polybasic acid or its anhydride, a conventionally well-known polybasic acid or its anhydride can be used. Specific examples include aromatic polycarboxylic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, tetrabromophthalic anhydride, methyl hymic anhydride, tetrachlorophthalic anhydride, and anhydrides thereof, hexahydrophthalic anhydride Acids, tetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, alicyclic carboxylic acids such as 1,3-cyclohexanedicarboxylic acid and their anhydrides, maleic anhydride, fumaric acid, succinic anhydride, adipic acid, sebacine Examples thereof include aliphatic polyvalent carboxylic acids such as acid and azelaic acid, and anhydrides thereof, pyromellitic anhydride, trimellitic anhydride, trifunctional or higher carboxylic acid such as methylcyclohexenedicarboxylic acid anhydride, alone or Two or more types can be used in combination.

  Examples of the compound (d) having one or more ethylenically unsaturated groups in the molecule include a compound having one carboxyl group and one or more ethylenically unsaturated groups, and a (meth) acrylic group having an isocyanate group. And a compound having one cyclic ether group and one or more ethylenically unsaturated groups, a compound having one hydroxyl group and one or more ethylenically unsaturated groups, and the like. Can be used in combination.

  Examples of the compound having one carboxyl group and one or more ethylenically unsaturated groups include acrylic acid, dimer of acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, crotonic acid, α -Half ester compounds of cyanocinnamic acid, cinnamic acid, (meth) acrylic acid caprolactone adduct, and saturated or unsaturated dibasic acid anhydride and (meth) acrylates having one hydroxyl group in one molecule Can be mentioned. Examples of (meth) acrylates having a hydroxyl group for producing a half ester compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, Examples include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and phenylglycidyl (meth) acrylate. 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, methylendomethylenetetrahydro Phthalic anhydride etc. are mentioned, It can use individually or in combination of 2 or more types.

  The (meth) acrylic monomer having an isocyanate group is not particularly limited as long as it is an isocyanate compound having one isocyanate group and one or more ethylenically unsaturated groups in one molecule. Specific examples include, for example, (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxyethoxyethyl isocyanate, bis (acryloxymethyl) ethyl isocyanate, or modified products thereof, alone or in combination of two or more. Can be used in combination. Commercially available products include “Karenz MOI” (methacryloyloxyethyl isocyanate), “Karenz AOI” (acryloyloxyethoxyethyl isocyanate), “Karenz MOI-EG” (methacryloyloxyethoxyethyl isocyanate), “Karenz MOI BM” (Karenz MOI isocyanate block), "Karenz MOI-BP" (Karenz MOI isocyanate block), and "Karenz BEI" (1,1-bis (acryloxymethyl) ethyl isocyanate) are commercially available from Showa Denko K.K. ing. These trade names are registered trademarks. Furthermore, a half urethane compound of a compound having one hydroxyl group and one or more ethylenically unsaturated groups in one molecule and a diisocyanate such as isophorone diisocyanate, toluylene diisocyanate, tetramethylxylene diisocyanate, hexamethylene diisocyanate is also used. can do.

  Examples of the compound having one cyclic ether group and one or more ethylenically unsaturated groups in one molecule include 2-hydroxyethyl (meth) acrylate glycidyl ether, 2-hydroxypropyl (meth) acrylate glycidyl ether, 3-hydroxy Propyl (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 Examples include ether or glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl acrylate, and the like can be used alone or in combination of two or more.

The compound having a hydroxyl group and an ethylenically unsaturated group is not particularly limited as long as it is a compound having one hydroxyl group and one or more ethylenically unsaturated groups in one molecule. Specific examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta ( Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate, and these can be used alone or in combination of two or more.
The (meth) acrylic monomer having a functional group capable of reacting with the alcohol or carboxylic acid as described above can be used alone or in combination of two or more.

  Examples of the monocarboxylic acid (e) having a phenol group include 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-amino-3-hydroxyphenylpropionic acid, 3,4-dihydroxyphenylalanine, Examples include 3,4,5-trihydroxybenzoic acid, and the like can be used alone or in combination of two or more.

  Examples of the compound (f) having a plurality of epoxy groups in the molecule include epoxidized vegetable oils such as Adekasizer O-130P, Adekasizer O-180A, Adekasizer D-32, and Adekasizer D-55 manufactured by ADEKA; JER (registered trademark) 828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, EHPE3150 manufactured by Daicel Chemical Industries, Epicron (registered trademark) 840, Epicron 850, Epicron 1050, Epicron 2055, Nippon Steel Chemical Co., Ltd. Epototo (registered trademark) YD-011, YD-013, YD-127, YD-128, manufactured by Dow Chemical Co., Ltd. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, BASF Japan Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo Co., Ltd. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. 664 etc. (all trade names) bisphenol A type epoxy resin; jERYL903 manufactured by Mitsubishi Chemical Corporation, Epicron 152, Epicron 165 manufactured by DIC Corporation, Epototo YDB-400, YDB-500 manufactured by Nippon Steel Chemical Co., Ltd., Dow Chemical D. E. R. 542, Araldide 8011 manufactured by BASF Japan, Sumi-epoxy ESB-400 and ESB-700 manufactured by Sumitomo Chemical Co., Ltd. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, Nippon Steel Chemical Co., Ltd. Epotot YDCN-701, YDCN-704, BASF Japan Araldide ECN1235, Araldide ECN1273, Araldide ECN1299 , Araldide XPY307, Nippon Kayaku Co., Ltd. EPPN (registered trademark) -201, EOCN (registered trademark) -1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumitomo Chemical Co., Ltd. Epoxy ESCN-195X, ESCN-220, A.A. E. R. ECN-235, ECN-299, etc. (both trade names) novolak epoxy resins; DIC Corporation Epicron 830, Mitsubishi Chemical Corporation jER807, Nippon Steel Chemical Co., Ltd. Epototo YDF-170, YDF-175, YDF -2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by BASF Japan (all trade names); water such as Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Nippon Steel Chemical Co., Ltd. Bisphenol A type epoxy resin; jER604 manufactured by Mitsubishi Chemical Co., Ltd., Epototo YH-434 manufactured by Nippon Steel Chemical Co., Ltd., Araldide MY720 manufactured by BASF Japan, Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. Product name) glycidylamine type epoxy resin; Araf made by BASF Japan Hydantoin type epoxy resin such as Dydo CY-350 (trade name); Celoxide (registered trademark) 2021 manufactured by Daicel Chemical Industries, araldide CY175, CY179 manufactured by BASF Japan, etc. (all trade names) YL-933 manufactured by Mitsubishi Chemical Corporation, T.M. manufactured by Dow Chemical Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names) Type or biphenol type epoxy resin or a mixture thereof; Nippon Kayaku EBPS-200, ADEKA EPX-30, DIC EXA-1514 (trade name) and other bisphenol S type epoxy resins; Bisphenol A novolac type epoxy resin such as jER157S (trade name); tetraphenylolethane type epoxy resin such as jERYL-931 manufactured by Mitsubishi Chemical Co., Ltd., Araldide 163 manufactured by BASF Japan Ltd. (both trade names); BASF Japan Araldide PT810 (trade name) manufactured by Nissan Chemical Industries Heterocyclic epoxy resin such as TEPIC (registered trademark) manufactured by Nihon Yushi Co., Ltd. Diglycidyl phthalate resin such as Bremer (registered trademark) DGT manufactured by Nippon Oil &Fats; Tetraglycidyl xylenoyl ethane such as ZX-1063 manufactured by Nippon Steel Chemical Resins; Naphthalene group-containing epoxy resins such as Nippon Steel Chemical Co., Ltd. ESN-190, ESN-360, DIC Corporation HP-4032, EXA-4750, EXA-4700; DIC Corporation HP-7200, HP-7200H, etc. Epoxy resin having dicyclopentadiene skeleton; Epoxy resin of glycidyl methacrylate copolymer such as CP-50S, CP-50M manufactured by NOF Corporation; Copolymer epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivative (For example, manufactured by Daicel Chemical Industries B-3600, etc.), CTBN modified epoxy resin (e.g., Nippon Steel Chemical Co. YR-102, YR-450, etc.) and others as mentioned, is not limited thereto. Among these, those that do not use epichlorohydrin in the process of epoxidation and epoxy resins that are high in purity and have a small amount of residual chlorine are preferred from the viewpoint of halogen-free. These epoxy resins can be used alone or in combination of two or more.

  In order to promote the depolymerization, a depolymerization catalyst can be used. Examples of the depolymerization catalyst include monobutyltin hydroxide, dibutyltin oxide, monobutyltin-2-ethylhexanoate, dibutyltin dilaurate, stannous oxide, tin acetate, zinc acetate, manganese acetate, cobalt acetate, and calcium acetate. , Lead acetate, antimony trioxide, tetrabutyl titanate, tetraisopropyl titanate and the like. The amount of these depolymerization catalysts used is usually in the range of 0.005 to 5 parts by mass, preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the polyester and polyhydric alcohol. is there.

  The photopolymerization initiator used in the present invention is at least selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. One kind of photopolymerization initiator can be preferably used.

（式中、Ｘは、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）を表し、Ｙ、Ｚはそれぞれ、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、結合か、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルを表し、ｐは０か１の整数である。） Examples of the oxime ester photopolymerization initiator include commercially available products such as CGI-325, Irgacure (registered trademark) OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, NCI-831 manufactured by Adeka Corporation, and the like. . Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.

(In the formula, X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms). A group, an amino group, an alkylamino group having 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 alkoxy group having 1 to 8 carbon atoms), And Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon number 1). Alkyl group having 1 to 8 alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms) Group or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms, or Represents an anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, and Ar is a bond or alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene , Anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and p is an integer of 0 or 1.)

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

  The blending amount of such an oxime ester photopolymerization initiator is preferably 0.02 to 10 wt% of the total amount of the composition. When it is less than 0.02 wt%, the photocurability on copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are deteriorated. On the other hand, when it exceeds 10 wt%, the light absorption on the coating film surface becomes intense and the deep curability tends to be lowered.

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

  Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6- And dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF, Irgacure 819 manufactured by BASF Japan, and the like.

  The blending amount of these α-aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.5 to 15 wt% of the total amount of the composition. If it is less than 0.5 wt%, the photocurability on copper is similarly insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are lowered. On the other hand, if it exceeds 15 wt%, the effect of reducing the outgas cannot be obtained, the light absorption on the surface of the coating film becomes intense, and the deep curability tends to decrease.

  In addition, examples of the photopolymerization initiator, photoinitiator assistant, and sensitizer that can be suitably used in the photocurable resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenones. Compounds, tertiary amine compounds, and xanthone compounds.

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

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

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

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

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

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

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

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

  The amount of such a thioxanthone compound is preferably 15 wt% or less of the total amount of the composition. When the blending amount of the thioxanthone compound exceeds 15 wt%, the thick film curability is lowered and the cost of the product is increased. More preferably, it is 10 wt% or less.

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

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

  As a compounding quantity of such a tertiary amine compound, it is preferable to set it as 0.1-15 wt% of the whole composition amount. When the compounding amount of the tertiary amine compound is less than 0.1 wt%, a sufficient sensitizing effect tends not to be obtained. If it exceeds 15 wt%, light absorption on the surface of the dried solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to be lowered.

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

  In addition, since these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, in some cases, the sensitivity is lowered, and the photopolymerization initiator, the photoinitiator assistant, and the sensitizer may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to improve the photoreactivity of the surface, change the resist line shape and opening to vertical, tapered, reverse taper, and processing accuracy of line width and opening diameter Can be improved.

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

  Further, examples of the heterocyclic compound having a mercapto group acting as a chain transfer agent include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, and 2-mercapto. -4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4- Butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) Ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5-va Lolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto- Examples include 5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, and 2-mercapto-6-hexanolactam.

  In particular, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2,4-triazole as a heterocyclic compound having a mercapto group that is a chain transfer agent that does not impair the developability of the photocurable resin composition 5-methyl-1,3,4-thiadiazole-2-thiol and 1-phenyl-5-mercapto-1H-tetrazole are preferred. These chain transfer agents can be used alone or in combination of two or more.

  Furthermore, for the purpose of improving photosensitivity, developability, heat resistance, and electrical characteristics, the photocurable resin composition of the present invention may contain a conventionally known carboxyl group-containing photosensitive resin. Although the weight average molecular weight of the carboxyl group-containing photosensitive resin to be used varies depending on the resin skeleton, it is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. If 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 may be poor, the film may be reduced during development, and the resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

The amount of such a carboxyl group-containing photosensitive resin is 50 wt% or less, preferably 10 to 40 wt% of the total composition.
Any of these carboxyl group-containing photosensitive resins can be used in the prior art, and can be used alone or in combination of two or more.

  In the photocurable resin composition of the present invention, a thermosetting component can be used to impart heat resistance. Examples of thermosetting components used in the present invention include amine resins such as melamine resins and benzoguanamine resins, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, bismaleimides, and oxazine compounds. In addition, known thermosetting resins such as oxazoline compounds and carbodiimide compounds can be used. Particularly preferred is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as “cyclic (thio) ether groups”) in the molecule.

  Such a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule includes either one of a three-, four- or five-membered cyclic ether group or a cyclic thioether group or two kinds of groups in the molecule. For example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a plurality of thioether groups in the molecule The compound which has this, ie, an episulfide resin etc. are mentioned.

  Examples of the polyfunctional epoxy compound include epoxidized vegetable oils such as Adekasizer O-130P, Adekasizer O-180A, Adekasizer D-32, and Adekasizer D-55 manufactured by ADEKA; jER (registered trademark) manufactured by Mitsubishi Chemical Corporation 828, jER834, jER1001, jER1004, EHPE3150 manufactured by Daicel Chemical Industries, Epicron (registered trademark) 840 manufactured by DIC, Epicron 850, Epicron 1050, Epicron 2055, Epotot (registered trademark) YD manufactured by Nippon Steel Chemical Co., Ltd. -011, YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, BASF Japan Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo Co., Ltd. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. 664 etc. (all trade names) bisphenol A type epoxy resin; jERYL903 manufactured by Mitsubishi Chemical Corporation, Epicron 152, Epicron 165 manufactured by DIC Corporation, Epototo YDB-400, YDB-500 manufactured by Nippon Steel Chemical Co., Ltd., Dow Chemical D. E. R. 542, Araldide 8011 manufactured by BASF Japan, Sumi-epoxy ESB-400 and ESB-700 manufactured by Sumitomo Chemical Co., Ltd. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, Nippon Steel Chemical Co., Ltd. Epotot YDCN-701, YDCN-704, BASF Japan Araldide ECN1235, Araldide ECN1273, Araldide ECN1299 , Araldide XPY307, Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumitomo Chemical Industries Sumi-Epoxy ESCN-195X, ESCN-220 Manufactured by Asahi Kasei Kogyo Co., Ltd. E. R. ECN-235, ECN-299, etc. (both trade names) novolak epoxy resins; DIC Corporation Epicron 830, Mitsubishi Chemical Corporation jER807, Nippon Steel Chemical Co., Ltd. Epototo YDF-170, YDF-175, YDF -2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by BASF Japan (all trade names); water such as Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Nippon Steel Chemical Co., Ltd. Bisphenol A type epoxy resin; jER604 manufactured by Mitsubishi Chemical Co., Ltd., Epototo YH-434 manufactured by Nippon Steel Chemical Co., Ltd., Araldide MY720 manufactured by BASF Japan, Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. Product name) glycidylamine type epoxy resin; Araf made by BASF Japan Hydantoin type epoxy resin such as Dydo CY-350 (trade name); Celoxide (registered trademark) 2021 manufactured by Daicel Chemical Industries, araldide CY175, CY179 manufactured by BASF Japan, etc. (all trade names) YL-933 manufactured by Mitsubishi Chemical Corporation, T.M. manufactured by Dow Chemical Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names) Type or biphenol type epoxy resin or a mixture thereof; Nippon Kayaku EBPS-200, ADEKA EPX-30, DIC EXA-1514 (trade name) and other bisphenol S type epoxy resins; Bisphenol A novolac type epoxy resin such as jER157S (trade name); tetraphenylolethane type epoxy resin such as jERYL-931 manufactured by Mitsubishi Chemical Co., Ltd., Araldide 163 manufactured by BASF Japan Ltd. (both trade names); BASF Japan Araldide PT810 made by Nissan, T made by Nissan Chemical Industries Heterocyclic epoxy resins such as PIC (both trade names); diglycidyl phthalate resins such as Blemmer (registered trademark) DGT manufactured by NOF Corporation; tetraglycidyl xylenoylethane resins such as ZX-1063 manufactured by Nippon Steel Chemical Co., Ltd. A naphthalene group-containing epoxy resin such as Nippon Steel Chemical Co., Ltd. ESN-190, ESN-360, DIC Corporation HP-4032, EXA-4750, EXA-4700; DIC Corporation HP-7200, HP-7200H, etc. Epoxy resin having cyclopentadiene skeleton; CP-50S, CP-50M glycidyl methacrylate copolymer epoxy resin such as Nippon Oil &Fats; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivative ( For example, Daicel Chemical Industries PB- 600, etc.), CTBN modified epoxy resin (e.g., Nippon Steel Chemical Co. YR-102, YR-450, etc.) and others as mentioned, is not limited thereto. These epoxy resins can 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 Industries, Ltd.) are preferable because they do not contain halogen ions as impurities. Also, epoxidized vegetable oils such as Adeka Sizer D-32, Adeka Sizer D-55, Adeka Sizer O-130P, Adeka Sizer O-180A (all manufactured by ADEKA) and the like are preferable because they do not contain halogen.

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

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

  The amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents, more preferably, relative to 1 equivalent of carboxyl groups in the composition. A range of 0.8 to 2.0 equivalents is appropriate. When the compounding amount of thermosetting components having multiple cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, resulting in decreased heat resistance, alkali resistance, electrical insulation, etc. Therefore, it is not preferable. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.

  Further, as another thermosetting component, a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be added. Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a plurality of blocked isocyanate groups in one molecule. The compound which has, ie, a blocked isocyanate compound, etc. are mentioned.

  As said polyisocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.

  The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.

  As such a blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As this isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.

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

  The blocked 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, Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate (registered trademark) 2512, Coronate 2513, Coronate 2520 (above, Nihon Polyurethane Industry Co., Ltd., product Name), B-830, B-815, B-846, B-870, B-874, B-882 (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (Asahi Kasei) Chemicals, product name)Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

The compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.
The blending amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is 1 to 50 wt%, more preferably 2 to 40 wt% of the total amount of the composition. When the blending amount is less than 1 wt%, it is not preferable because sufficient toughness of the coating film cannot be obtained. On the other hand, when it exceeds 50 wt%, storage stability falls and it is not preferable.

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

  Examples of these commercially available products include Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202. 1156, 1158, 1123, 1170, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak (registered trademark) Mx-750, Mx-032, Mx-270 Mx-280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390 , Mw-100LM, Mw-750LM, and the like (manufactured by Sanwa Chemical Co., Ltd.). The said thermosetting component can be used individually or in combination of 2 or more types.

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

  The amount of these thermosetting catalysts to be blended is a normal quantitative ratio, and is preferably 0.1 to 100 parts by mass of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule. It is 20 mass parts, More preferably, it is 0.5-15.0 mass parts.

  The photocurable resin composition of this invention can mix | blend a coloring agent. As the colorant, conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.

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

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

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

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

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

  The mixing ratio of the colorant as described above is not particularly limited, but 5 wt% or less, more preferably 0.1 to 3 wt% is sufficient in the solid content of the composition.

  The photocurable resin composition of the present invention can be blended with a filler as necessary in order to increase the physical strength of the coating film. As such a filler, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica and talc are preferably used. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers. The blending amount of the filler is preferably 75 wt% or less, more preferably 0.1 to 60 wt% of the total amount of the composition. When the blending amount of the filler exceeds 75 wt% of the total amount of the composition, the viscosity of the insulating composition becomes high, the coating and moldability are lowered, and the cured product becomes brittle.

Furthermore, the photocurable resin composition of the present invention uses an organic solvent for the synthesis of the resin used in the present invention, for the preparation of the composition, or for the viscosity adjustment for application to a substrate or a carrier film. be able to.
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Such as propylene glycol butyl ether acetate, methyl 2-hydroxyisobutyrate Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

  The photo-curable resin composition of the present invention may further comprise, as necessary, known and conventional thickeners such as known thermal polymerization inhibitors, finely divided silica, organic bentonite, and montmorillonite, silicone-based, fluorine-based, polymer-based, etc. The known antifoaming agent and / or leveling agent, imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, rust inhibitors, and the like can be blended.

  The photocurable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using, for example, the organic solvent, and on a substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method. A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (temporary drying). Moreover, a resin insulation layer can be formed by apply | coating the said composition on a carrier film, and drying and winding up as a film together on a base material. Thereafter, by a contact method (or non-contact method), exposure is selectively performed with an active energy ray through a photomask having a pattern formed thereon or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (eg, 0.3 The resist pattern is formed by development with a 3 wt% sodium carbonate aqueous solution. Further, in the case of a composition containing a thermosetting component, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group-containing resin and the carboxyl group of the carboxyl group-containing photosensitive resin A cured coating having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties due to reaction of thermosetting components having a plurality of cyclic ether groups and / or cyclic thioether groups in the molecule. A film can be formed. In addition, even when it does not contain a thermosetting component, by performing heat treatment, the ethylenically unsaturated bond of the photocurable component remaining in an unreacted state at the time of exposure undergoes thermal radical polymerization, and the coating film characteristics are improved. Therefore, heat treatment (thermosetting) may be performed depending on the purpose and application.

  As the substrate, in addition to a printed circuit board and a flexible printed circuit board in which circuits are formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminate of all grades (FR-4 etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, PET A film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.

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

  After applying the photocurable resin composition of the present invention and evaporating and drying as follows, the obtained coating film is exposed (irradiated with active energy rays). In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.

As the exposure apparatus used for the active energy ray irradiation, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer), an exposure apparatus equipped with a metal halide lamp, and an (ultra) high pressure mercury lamp. , An exposure machine equipped with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (super) high pressure mercury lamp. As the active energy ray, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. Further, the exposure amount varies depending the thickness or the like, generally 5~800mJ / cm ^2, preferably be in the range of 5~500mJ / cm ^2. As the direct drawing device, for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any device may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .

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

  The photo-curable resin composition of the present invention is in the form of a dry film having a solder resist layer formed by applying and drying a solder resist in advance on a film of polyethylene terephthalate or the like in addition to the method of directly applying the liquid curable resin composition to a substrate. Can also be used. The case where the curable resin composition of this invention is used as a dry film is shown 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. For the solder resist layer, the alkali-developable photo-curable resin composition is uniformly applied to a carrier film or a cover film with a thickness of about 10 to 150 μm using a blade coater, lip coater, comma coater, film coater, etc., and dried. Formed. After forming a solder resist layer on the carrier film, a cover film is laminated thereon, or a solder resist layer is formed on the cover film, and this laminate is laminated on the carrier film to obtain a dry film.

As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used.
As the cover film, a polyethylene film, a polypropylene film, or the like can be used.

  To produce a protective film (permanent protective film) on a printed wiring board using a dry film, peel off the cover film, layer the solder resist layer and the substrate on which the circuit is formed, and bond them together using a laminator, etc. A solder resist layer is formed on the formed substrate. If the formed solder resist layer is exposed, developed, and heat cured in the same manner as described above, a cured coating film can be formed. The carrier film may be peeled off either before exposure or after exposure.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following description, “parts” and “%” are based on mass unless otherwise specified.

(B-1) Carboxylic acid resin synthesis example 1
384 parts of PET flakes (Mitsubishi Chemical Co., Ltd .: Novavex, IV value 1.1) were charged in a 1000 ml four-necked round bottom separable lasco equipped with a stirrer, nitrogen introduction tube, and cooling tube, and the inside of the flask was made a nitrogen atmosphere. Then, it was immersed in a salt bath heated to 300 ° C. When PET was dissolved, stirring was started and 1.6 parts of dibutyltin oxide was added. Next, 134 parts of trimethylolpropane previously heated and dissolved at 130 ° C. was added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Next, the salt bath was replaced with an oil bath that was previously heated to 240 ° C., and the temperature in the flask was kept at 220 ° C. ± 10 ° C. for 5 hours. Next, 518 parts of this reaction product was placed in a 1000 mL four-necked flask equipped with a stirrer, an air introduction tube, a fractionation tube, and a cooling tube, 81 parts of acrylic acid, 2.4 parts of paratoluenesulfonic acid, and paramethoxyphenol 0. 8 parts, 212 parts of methyl isobutyl ketone and 112 parts of toluene were stirred and dissolved uniformly, then immersed in an oil bath heated to 115 ° C. ± 5 ° C., and the reaction was continued for a predetermined time. After completion of the reaction, the acid value of the reaction solution was measured, and an acid equivalent alkaline aqueous solution was added to the flask and stirred to neutralize. Next, brine (20 wt%) was added and stirred. Thereafter, the solution was transferred to a separatory funnel, the same amount of methyl ethyl ketone as the reaction solution was added, and the aqueous phase was discarded. The oil phase was washed twice with brine (5 wt%) and the aqueous phase was discarded. Furthermore, 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, concentration was performed with an evaporator to obtain a PET-containing acrylate resin. Next, a 300 mL four-necked round bottom flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube was charged with 50 parts of PET-containing acrylate resin and 27 parts of carbitol acetate, and the atmosphere in the flask was changed to 80 ° C. It was immersed in an oil bath heated to ± 5 ° C. Next, 20 parts of tetrahydrophthalic anhydride was added every 2.5 hours while gradually adding a carbitol acetate solution prepared by dissolving 0.8 part of triphenylphosphine and 0.4 part of methoquinone in 10 parts of carbitol acetate. The reaction was carried out for 10 hours while adding in 4 portions to obtain a resin solution of carboxyl group-containing acrylate having a solid content of 65%, a solid content acid value of 128 mgKOH / g, and a chlorine concentration of 20 ppm or less. This resin solution is referred to as B-1.

(B-2) Carboxylic acid resin synthesis example 2
A 500 ml four-necked round bottom separable lasco fitted with a stirrer, a nitrogen inlet tube, and a condenser tube is 62 parts 1,3-propylene glycol, 7.8 parts trimethylolpropane, 0.77 parts dibutyltin oxide, 40.6 parts isophthalic acid Then, 64 parts of PET flakes (Mitsubishi Chemical Corporation: Novavex, IV value 1.1) were charged, the inside of the flask was made a nitrogen atmosphere, and then immersed in an oil bath heated to 130 ° C. When the contents were dissolved, the temperature was raised to 180 ° C. Next, the temperature was raised to 235 ° C., and the reaction was continued for 1 hour. When 1 hour had passed, 128 parts of PET flakes (Mitsubishi Chemical Corporation: Novavex, IV value 1.1) and 81.3 parts of isophthalic acid were sequentially added, and the reaction was continued for 14 hours until it became a transparent liquid.
Next, while maintaining the flask internal temperature at 200 ° C., stirring was started, and 96 parts of trimellitic acid was added and dissolved. Thereafter, the reaction was continued for 8 hours. Next, the temperature of the flask was lowered to 110 ° C., 1.02 part of triphenylphosphine, 0.51 part of methoquinone, and 287.7 parts of carbitol acetate were added and stirred. After continuing the stirring, 51 parts of glycidyl methacrylate was added and allowed to react for 6 hours. Thus, a carboxyl group-containing photosensitive compound varnish having a solid content of 65% and a solid content acid value of 90 mgKOH / g was obtained. Hereinafter, this resin solution is referred to as B-2.

(B-3) Carboxylic acid resin synthesis example 3
192 parts of PET flakes (Mitsubishi Chemical Corporation: Novavex, IV value 1.1) were charged in a 500 ml four-necked round bottom separable lasco fitted with a stirrer, nitrogen introduction tube, and cooling tube, and the inside of the flask was made a nitrogen atmosphere. Then, it was immersed in a salt bath heated to 300 ° C. When PET was dissolved, stirring was started and 1.6 parts of dibutyltin oxide was added. Next, 134 parts of trimethylolpropane previously heated and dissolved at 130 ° C. was added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Next, the oil bath was preliminarily heated to 240 ° C. from the salt bath, the flask internal temperature was kept at 220 ° C. ± 10 ° C., the reaction was performed for 5 hours, and then cooled to room temperature. Next, 121.6 parts of tetrahydrophthalic anhydride (THPA) and 240 parts of carbitol acetate were charged, the inside of the flask was made a nitrogen atmosphere, and then immersed in an oil bath heated to 125 ± 5 ° C. Stirring was started gradually and the reaction was carried out for 3 hours to obtain a carboxylic acid resin having a nonvolatile content of 65%, a solid content acid value of 103 mgKOH / g, and a chlorine concentration of 20 ppm or less. This resin solution is referred to as B-3.

Example of Synthesis of Carboxyl Group-Containing Photosensitive Resin Orthocresol Novolac Type Epoxy Resin (600, DIC Corporation, EPICLON N-695, Softening Point 95 ° C., Epoxy Equivalent 214, Average Functional Group Number 7.6) 1070 with 600 parts of diethylene glycol monoethyl ether acetate Parts (the number of glycidyl groups (total number of aromatic rings): 5.0 mol), 360 parts (5.0 mol) of acrylic acid, and 1.5 parts of hydroquinone were heated and stirred at 100 ° C., and uniformly dissolved. Next, 4.3 parts of triphenylphosphine was added, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. To the obtained reaction liquid, 415 parts of aromatic hydrocarbon (Sorvesso 150) and 456.0 parts (3.0 mol) of tetrahydrophthalic anhydride were reacted, and reacted at 110 ° C. for 4 hours. After cooling, solid content 65 %, A solid content acid value of 89 mgKOH / g, and a chlorine concentration of 400 ppm was obtained. This resin solution is referred to as R-1.

(C) Polyester acrylate synthesis example 192 parts of PET flake (Mitsubishi Chemical Co., Ltd .: Novavex (trade name)) was charged into a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen inlet tube, and a cooling tube, and the flask was filled with nitrogen. After setting the atmosphere, it was immersed in a salt bath heated to 300 ° C. When the PET flakes were dissolved, stirring was started and 0.65 part of dibutyltin oxide was added.
Next, 134 parts of trimethylolpropane previously heated and dissolved at 130 ° C. was added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Next, the salt bath was replaced with an oil bath that had been heated to 240 ° C. in advance, and the temperature in the flask was kept at 220 ° C. ± 10 ° C. for 5 hours. The reaction product was transparent yellow and soft viscous at room temperature.
To 100 parts of the obtained reaction product, 37 parts of toluene and 74 parts of methyl isobutyl ketone were introduced and mixed. Next, 65 parts of acrylic acid, 1.94 parts of paratoluenesulfonic acid, and 0.26 part of paramethoxyphenol were added and reacted at 110 ° C. for 100 hours, and cooled to room temperature. The acid value of the obtained reaction solution was measured, and an acid equivalent alkaline aqueous solution was added to the flask and stirred to neutralize. Next, 50 parts of brine was added and stirred.
Thereafter, the solution was transferred to a separating funnel, the aqueous phase was discarded, and the oil phase was washed twice with 100 parts of a 5 wt% NaCl solution. After washing, the solvent was distilled off with an evaporator to obtain a reaction product having a nonvolatile content of 100%. The obtained reaction product was a brown transparent soft liquid at room temperature. This resin solution is referred to as C-1.

(D-1) Epoxy resin synthesis example 1
192 parts of PET flakes (Mitsubishi Chemical Corporation: Novavex, IV value 1.1) were charged in a 500 ml four-necked round bottom separable lasco fitted with a stirrer, nitrogen introduction tube, and cooling tube, and the inside of the flask was made a nitrogen atmosphere. Then, it was immersed in a salt bath heated to 300 ° C. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Subsequently, 45 parts of trimethylolpropane previously heated and dissolved at 130 ° C. was added little by little while taking care not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Next, the oil bath was preliminarily heated to 240 ° C. from the salt bath, and the temperature in the flask was kept at 220 ° C. ± 10 ° C. for 5 hours, followed by cooling to room temperature. 200 parts of the depolymer obtained in this manner was charged into a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen introduction tube and a cooling tube, and the atmosphere in the flask was changed to 145 ° C. ± 5 ° C. Immerse in a heated oil bath. About 30 minutes after starting stirring, 83 parts of tetrahydrophthalic anhydride was added and stirring was continued. Thus, a carboxylic acid resin having an acid value of 112 mgKOH / g was obtained. Next, 40 parts of this carboxylic acid resin was charged into a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, and further YD-825GS (manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent of 185 g / eq. The chlorine concentration was 160 ppm), the flask was filled with a nitrogen atmosphere, the temperature of the oil bath was gradually raised, and after the contents were dissolved, the temperature of the oil bath was raised to 110 ° C. ± 5 ° C. and the reaction was continued. , Epoxy equivalent 421 g / eq. An epoxidized resin having a chlorine concentration of 93 ppm was obtained. This is referred to as epoxy resin D-1.

(D-2) Epoxy resin synthesis example 2
192 parts of PET flakes (Mitsubishi Chemical Corporation: Novavex, IV value 1.1) were charged in a 500 ml four-necked round bottom separable lasco fitted with a stirrer, nitrogen introduction tube, and cooling tube, and the inside of the flask was made a nitrogen atmosphere. Then, it was immersed in a salt bath heated to 300 ° C. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Next, 104 parts of neopentyl glycol, which was heated and dissolved in advance at 130 ° C., was added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Next, the oil bath was preliminarily heated to 240 ° C. from the salt bath, and the temperature in the flask was kept at 220 ° C. ± 10 ° C. for 5 hours, followed by cooling to room temperature. 118 parts of the depolymer thus obtained was charged into a 500 ml four-necked round-bottom separable lasco equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, and the atmosphere in the flask was changed to a nitrogen atmosphere. Then, o-hydroxybenzoic acid 110 Part and 0.5 part of dibutyltin oxide were charged, and the inside of the flask was made a nitrogen atmosphere. Condensed water was removed over about 4 to 6 hours while gradually heating the hot water bath to 200 ° C., and when the acid value was sufficiently lowered, the oil bath was lowered and the contents of the flask were taken out to obtain a phenol resin. Next, 45.1 parts of this phenol resin was charged into a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, and further YD-825GS (manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent of 185 g / eq). And 66.3 parts of chlorine concentration (160 ppm), the atmosphere in the flask was changed to a nitrogen atmosphere, the oil bath was gradually heated, and after the contents were dissolved, the oil bath was heated to 110 ° C. ± 5 ° C. The reaction was continued and an epoxy equivalent of 447 g / eq. An epoxidized resin having a chlorine concentration of 95 ppm was obtained. This is referred to as epoxy resin D-2.

Examples 1-13 and Comparative Examples 1-2
Using the resins of the above synthesis examples, blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1 below, premixed with a stirrer, kneaded with a three-roll mill, and used for solder resist A photosensitive resin composition was prepared.

Performance evaluation:
<Polyester-derived compound content>
Table 2 shows the contents (in the organic component) of the compounds derived from the general formula (1) in the compositions of the examples and comparative examples.

<Optimum exposure amount>
A circuit pattern substrate having a copper thickness of 35 μm is polished with buffalo, washed with water and dried, and then the photosensitive resin compositions of the examples and comparative examples are applied to the entire surface by a screen printing method, and a hot air circulation drying oven at 80 ° C. And dried for 60 minutes. After drying, exposure is performed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and development (30 ° C., 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution) is performed at 60. When the pattern of the step tablet remaining when performing in seconds was 7 steps, the optimum exposure amount was set.

<Developability>
The photosensitive resin compositions of the examples and comparative examples were applied on a copper solid substrate by screen printing so that the film thickness after drying was about 25 μm, and dried for 30 minutes in a hot air circulation drying oven at 80 ° C. I let you. After drying, development was performed with a 1 wt% Na ₂ CO ₃ aqueous solution, and the time until the dried coating film was removed was measured with a stopwatch.

<Dry touch dryness>
The photosensitive resin compositions of the examples and comparative examples were each applied onto the patterned copper foil substrate by screen printing, dried in a hot air circulating drying oven at 80 ° C. for 30 minutes, and allowed to cool to room temperature. A PET film was pressed against this substrate, and then the sticking state of the film when the negative film was peeled off was evaluated. The judgment criteria are as follows.
(Double-circle): When peeling a film, there is no resistance and a trace is not left in a coating film.
○: When the film is peeled off, there is no resistance, but the coating film has a slight mark.
(Triangle | delta): When peeling a film, there exists resistance slightly and the coating film has a trace.
X: When the film is peeled off, there is resistance and the coating film is clearly marked.

<Resolution>
The circuit pattern substrates of 300/300 μm in line / space and 35 μm in copper thickness were coated with the photosensitive resin compositions of Examples and Comparative Examples by buffing, washed with water, dried and then applied by screen printing. It was dried for 30 minutes in a hot air circulation drying oven. After drying, exposure was performed using an exposure apparatus equipped with a high-pressure mercury lamp. For the exposure pattern, a negative was used to draw a 20/30/40/50/60/70/80/90/100 μm line in the space. The active energy ray was irradiated so that the exposure amount became the optimal exposure amount of the photosensitive resin composition. After the exposure, a 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 cured at 150 ° C. for 60 minutes to obtain a cured coating film. It determined using the optical microscope which adjusted the minimum residual line of the cured coating film of the obtained photosensitive resin composition for solder resists 200 times, and made this resolution.

<Halogen content>
Using the resin solutions obtained in each of the above synthesis examples, the various components shown in Table 1 above were blended in the proportions (parts by mass) shown in Table 1, premixed with a stirrer, and then kneaded with a three-roll mill. A photosensitive resin composition was prepared. By using the flask combustion treatment ion chromatograph method based on the JPCA standard, the halogen ion impurity content (total of chloride and bromide) was quantified for the obtained photosensitive resin composition. When the halogen ion concentration is 20 ppm or less (quantitative limit), the notation is “−”. The results are shown in Table 2.

Characteristic test:
The compositions of Examples and Comparative Examples were applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. This substrate is exposed to a solder resist pattern at an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and developed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. for 60 seconds under a spray pressure of 0.2 MPa. And a resist pattern was obtained. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.
A: Peeling is not observed even after 10 seconds of immersion for 6 or more times.
○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more.
(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated 3 times or more.
X: The resist layer swells and peels off within 3 times for 10 seconds.

<Alkali resistance>
The evaluation substrate was immersed in a 10 wt% NaOH aqueous solution at room temperature for 30 minutes, and soaking, dissolution of the coating film, and peeling by tape beer were confirmed. The judgment criteria are as follows.
○: No soaking, melting or peeling.
Δ: Slight penetration, dissolution or peeling is confirmed.
X: Significant infiltration, dissolution or peeling.

<Peelability>
The evaluation substrate was immersed in a 10 wt% NaOH aqueous solution at 60 ° C. to evaluate whether the solder resist layer could be peeled from the substrate. The evaluation criteria are as follows.
A: Peeling is possible by immersion for 15 minutes.
○: Peeling is possible by immersion for 30 minutes.
Δ: Some residue is observed after 60 minutes of immersion.
X: Unpeelable.

<Electrode discoloration resistance>
An evaluation substrate was produced under the above conditions using a comb / electrode pattern of line / space = 50/50 μm instead of the copper foil substrate, and the comb electrode was formed at 121 ° C. and 97% R.D. H. A bias voltage of DC 30 V was applied under the warming and humidification conditions, and the degree of discoloration of the coating film around the electrode after 100 hours was evaluated. The judgment criteria are as follows.
○: No discoloration of the coating film.
(Triangle | delta): Discoloration of a coating film is confirmed slightly.
X: Discoloration of coating film is present.

<Dry film production>
After appropriately diluting each of the photosensitive resin compositions for solder resist of Example 1 and Comparative Example 1 with methyl ethyl ketone, using an applicator, a PET film (Toray FB-50: Toray FB-50: having a thickness of 30 μm after drying) 16 μm) and dried at 40 to 100 ° C. to obtain a dry film.

<Board fabrication>
After the circuit-formed substrate is buffed, the dry film produced by the above method is pressurized using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho): 0.8 MPa, 70 ° C., 1 minute, vacuum degree The substrate (unexposed substrate) having an unexposed solder resist layer was obtained by heat lamination under the condition of 133.3 Pa. Each test of the obtained substrate was carried out in the same manner as in the evaluation method described above, such as optimum exposure, developability, resolution, solder heat resistance, alkali resistance, peelability, and electrode discoloration resistance.
The evaluation results are shown in Table 2.

As is clear from the results shown in Table 2 above, Comparative Examples 1 and 2 using a photocurable resin composition not containing the polyester-derived compound (carboxylic acid resin, poly (meth) acrylate and epoxy resin) of the present invention. Then, it was impossible to peel the solder resist layer from the substrate by the immersion treatment in a 10 wt% NaOH aqueous solution at 60 ° C.
On the other hand, the photocurable resin composition of the present invention of Examples 1 to 13 has both general alkali resistance and peelability by an alkaline aqueous solution, and when used as a solder resist, a solder resist forming step. It is possible to reuse the substrate by peeling and cleaning only the solder resist cured film from the printed wiring board that is normally discarded due to a defect caused by the above.

Claims (5)

Containing derived Ru (D) an epoxy resin of a compound containing a structure represented by the following following general formula (1), wherein the compound containing a structure represented by (D) an epoxy resin alone or the general formula (1) 20 wt% or more based on organic matter in the composition in combination with other compounds derived from (provided that at least one of (B) carboxylic acid resin and (C) poly (meth) acrylate) A photocurable resin composition comprising a proportion.

(Wherein R ¹ represents an (m + 1) -valent polyhydric alcohol derivative, and R ² represents any of 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 integers of 1 or more and less than 10, and l is 0 or an integer of 1 or more.) Furthermore, both are derived from a compound containing the structure represented by the general formula (1), and contain at least one of (B) carboxylic acid resin and (C) poly (meth) acrylate. The photocurable resin composition according to claim 1. The photocurable dry film obtained by apply | coating and drying the photocurable resin composition of Claim 1 or 2 on a film. The photocurable resin composition according to claim 1 or 2, or photocurable resin composition constituting the photocurable dry film according to claim 3, patterned cured product. The printed wiring board which has a pattern-shaped cured film of the photocurable resin composition of Claim 1 or 2, or the photocurable resin composition which comprises the photocurable dry film of Claim 3 .