Photosensitive resin composition

Abstract

The present invention provides a photosensitive resin composition having photosensitivity, excellent insulation reliability, and physical properties suitable for a stacked layer (interlayer insulation layer) of a multilayer printed wiring board. The photosensitive resin composition contains: (A) an epoxy resin, (B) one or more curing agents selected from active ester curing agents, cyanate curing agents, and benzoxazine curing agents, and (C) a compound having a (meth)acrylate structure.

Description

[0001] This application is a divisional application of the Chinese patent application with application number 201480036156.3, application date June 26, 2014, and invention name “Photosensitive resin composition”. Technical Field

[0002] The present invention relates to a photosensitive resin composition and more particularly to a photosensitive resin composition suitable for use in an interlayer insulating layer of a multilayer printed wiring board. Background Art

[0003] The mainstream of conventional photosensitive resin compositions is alkali-developable, and acrylates containing anhydride groups or carboxyl groups are used for development. However, since anhydride groups or carboxyl groups are easily thermally degraded, the cured product using such acrylates cannot obtain sufficient physical properties, and when anhydride groups or carboxyl groups are present, there are limitations in forming an insulating layer with high insulation reliability.

[0004] Therefore, for example, Patent Document 1 discloses a photosensitive resin composition for MEMS containing a specific photocationic polymerization initiator and a specific epoxy resin, but its use is limited to MEMS use, and its insulation reliability is insufficient, so it is particularly unable to exert sufficient performance as a stacking layer of a multilayer printed wiring board. In addition, Patent Document 2 discloses a photosensitive resin composition for a protective film of a printed wiring board for semiconductor packaging, but its insulation reliability is insufficient, and its use is limited to a protective film, and it still cannot exert sufficient performance as a stacking layer of a multilayer printed wiring board.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2009-263544

[0008] Patent document 2: International Publication No. 2010 / 026927. Summary of the invention

[0009] Problems to be solved by the invention

[0010] Therefore, an object of the present invention is to provide a resin composition which has photosensitivity, excellent insulation reliability, and physical properties suitable for a build-up layer (interlayer insulation layer) of a multilayer printed wiring board.

[0011] Means for solving problems

[0012] The present inventors have found that the above-mentioned problems can be solved by using a photosensitive resin composition containing (A) an epoxy resin, (B) one or more curing agents selected from active ester curing agents, cyanate curing agents and benzoxazine curing agents, and (C) a compound having a (meth)acrylate structure, thereby completing the present invention.

[0013] That is, the present invention includes the following contents:

[0014] [1] A photosensitive resin composition comprising:

[0015] (A) Epoxy resin,

[0016] (B) at least one curing agent selected from the group consisting of an active ester curing agent, a cyanate curing agent, and a benzoxazine curing agent, and

[0017] (C) a compound having a (meth)acrylate structure;

[0018] [2] The photosensitive resin composition of [1], wherein the epoxy resin (A) contains both an epoxy resin that is liquid at 20°C and an epoxy resin that is solid at 20°C;

[0019] [3] The photosensitive resin composition according to [1] or [2], wherein the content of the component (A) is 3 to 50% by mass when the non-volatile component of the photosensitive resin composition is 100% by mass;

[0020] [4] The photosensitive resin composition according to any one of [1] to [3], wherein the content of the component (B) is 1 to 30% by mass when the non-volatile component of the photosensitive resin composition is 100% by mass;

[0021] [5] The photosensitive resin composition according to any one of [1] to [4], wherein the component (C) comprises a polymer having a (meth)acrylate structure and having a weight average molecular weight of 500 to 100,000;

[0022] [6] The photosensitive resin composition according to any one of [1] to [5], wherein the component (C) has an epoxy group;

[0023] [7] The photosensitive resin composition according to any one of [1] to [6], wherein the acid value of the component (C) is 20 mgKOH / g or less;

[0024] [8] The photosensitive resin composition according to any one of [1] to [7], wherein the content of the component (C) is 1 to 25% by mass when the non-volatile component of the photosensitive resin composition is 100% by mass;

[0025] [9] The photosensitive resin composition according to any one of [1] to [8], further comprising (D) a photopolymerization initiator;

[0026]

[10] The photosensitive resin composition according to any one of [1] to [9], further comprising (E) an inorganic filler;

[0027]

[11] The photosensitive resin composition of

[10] , wherein the content of the (E) inorganic filler is 10 to 85% by mass when the non-volatile component of the photosensitive resin composition is 100% by mass;

[0028]

[12] The photosensitive resin composition of

[10] , wherein the content of the (E) inorganic filler is 50 to 85% by mass when the non-volatile component of the photosensitive resin composition is 100% by mass;

[0029]

[13] The photosensitive resin composition according to any one of [1] to

[12] , which is used for an interlayer insulating layer of a multilayer printed wiring board;

[0030]

[14] The photosensitive resin composition according to any one of [1] to

[13] , wherein a cured product of the photosensitive resin composition has a dielectric loss tangent of 0.005 to 0.05;

[0031]

[15] The photosensitive resin composition according to any one of [1] to

[14] , wherein the water absorption of the cured product of the photosensitive resin composition is 0.01 to 3%;

[0032]

[16] A photosensitive film with a support, comprising the photosensitive resin composition according to any one of [1] to

[15] .

[0033]

[17] A multilayer printed wiring board comprising a cured product of the photosensitive resin composition according to any one of [1] to

[15] .

[0034]

[18] A semiconductor device, characterized by using the multilayer printed wiring board described in

[17] .

[0035] Effects of the Invention

[0036] According to the present invention, a resin composition having photosensitivity, excellent insulation reliability, and physical properties suitable for a buildup layer of a multilayer printed wiring board can be provided. Furthermore, the photosensitive resin composition of the present invention can provide a buildup layer having excellent dielectric properties and suppressed power consumption, and can provide a buildup layer having excellent water resistance and heat resistance. DETAILED DESCRIPTION

[0037] The present invention is described in detail below according to the preferred embodiments of the present invention.

[0038] [Photosensitive resin composition]

[0039] The photosensitive resin composition of the present invention is characterized by comprising (A) an epoxy resin, (B) one or more curing agents selected from active ester curing agents, cyanate curing agents and benzoxazine curing agents, and (C) a compound having a (meth)acrylate structure.

[0040] The components (A) to (C) contained in the resin composition of the present invention will be described below.

[0041] <(A)Component>

[0042] Component (A) is an epoxy resin.

[0043] The epoxy resin is not particularly limited, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, dicyclopentadiene epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidylamine epoxy resin, glycidylester epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol epoxy resin, naphthylene ether epoxy resin, and trimethylol epoxy resin. The epoxy resins may be used alone or in combination of two or more.

[0044] The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, it is preferred that at least 50% by mass is an epoxy resin having two or more epoxy groups in one molecule.

[0045] In addition, it is preferred to contain an epoxy resin that is liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20°C (hereinafter referred to as "solid epoxy resin"). As epoxy resins, by using a liquid epoxy resin and a solid epoxy resin in combination, a resin composition having excellent flexibility can be obtained. In addition, the breaking strength of the insulating layer formed by curing the resin composition is also improved.

[0046] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, or naphthalene type epoxy resin is preferred, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, or naphthalene type epoxy resin is more preferred. As specific examples of the liquid epoxy resin, DIC (co) "HP4032", "HP4032D", "EXA4032SS", "HP4032SS" (naphthalene type epoxy resin), Mitsubishi Chemical (co) "jER828EL" (bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), Nippon Steel Chemical (co) "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) and the like can be cited. As the liquid epoxy resin, "HP4032SS" (naphthalene type epoxy resin) and "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) are particularly preferred. The liquid epoxy resin may be used alone or in combination of two or more.

[0047] As the solid epoxy resin, preferred are tetrafunctional naphthalene-type epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol epoxy resins, naphthol novolac-type epoxy resins, biphenyl-type epoxy resins, or naphthylene ether-type epoxy resins; more preferred are tetrafunctional naphthalene-type epoxy resins, biphenyl-type epoxy resins, or naphthylene ether-type epoxy resins; and further preferred are biphenyl-type epoxy resins. Specific examples of solid epoxy resins include "HP-4700", "HP-4710" (quadrifunctional naphthalene type epoxy resins), "N-690" (cresol novolac type epoxy resins), "N-695" (cresol novolac type epoxy resins), "HP7200", "HP7200H", "HP7200K-65I" (dicyclopentadiene type epoxy resins), "EXA7311", "EXA7311-G3", "HP6000" (naphthylene ether type epoxy resins), "EPP7000" (epoxy resins) manufactured by Nippon Kayaku Co., Ltd., and "EPP7000" (epoxy resins). N-502H" (trisphenol epoxy resin), "NC7000L" (naphthol novolac epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl epoxy resin), "ESN475" (naphthol novolac epoxy resin), "ESN485" (naphthol novolac epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd., "YX4000H", "YL6121" (biphenyl epoxy resin), "YX4000HK" (biphenyl epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., etc. Particularly preferred are "YX4000HK" (biphenyl epoxy resin), "NC3000L" (biphenyl epoxy resin) manufactured by Nippon Kayaku Co., Ltd., and "HP7200H" (dicyclopentadiene epoxy resin) manufactured by DIC Corporation. The solid epoxy resin may be used alone or in combination of two or more.

[0048] When a liquid epoxy resin and a solid epoxy resin are used together as the epoxy resin, the mass ratio of the liquid epoxy resin and the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1:0.1 to 1:4. By making the mass ratio of the liquid epoxy resin to the solid epoxy resin in the above range, the following effects can be obtained: i) when used in the form of an adhesive film, appropriate adhesion can be obtained, ii) when used in the form of an adhesive film, sufficient flexibility and improved handleability can be obtained, and iii) an insulating layer with sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii) above, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1:0.3 to 1:3.5, further preferably in the range of 1:0.6 to 1:3, and particularly preferably in the range of 1:0.8 to 1:2.5.

[0049] When the nonvolatile component in the photosensitive resin composition is 100 mass %, the content of the epoxy resin is preferably 3 mass % to 50 mass %, more preferably 5 mass % to 45 mass %, further preferably 7 mass % to 35 mass %, particularly preferably 8 mass % to 20 mass %.

[0050] The epoxy equivalent of the epoxy resin is preferably 50 to 3000, more preferably 80 to 2000, and even more preferably 110 to 1000. By setting the epoxy equivalent within this range, the crosslinking density of the cured product is sufficient, and an insulating layer with excellent heat resistance is obtained. It should be noted that the epoxy equivalent can be measured according to JIS K7236 and is the mass of a resin containing 1 equivalent of epoxy groups.

[0051] <(B) Ingredient>

[0052] The component (B) is one or more curing agents selected from the group consisting of active ester curing agents, cyanate ester curing agents, and benzoxazine curing agents.

[0053] -Active ester curing agent-

[0054] The active ester curing agent used in the photosensitive resin composition of the present invention can improve the heat resistance, dielectric properties, and water resistance of the cured product, and in particular, the dielectric properties and water resistance are excellent. The active ester curing agent is not particularly limited, and preferably a compound having two or more active ester groups in one molecule. As the active ester curing agent, it is generally preferred to use a compound having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds.

[0055] From the viewpoint of improving the heat resistance when used as a cured product, as an active ester curing agent, it is preferably an active ester compound obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxyl compound and / or a thiol compound, more preferably an active ester compound obtained by a carboxylic acid compound and a hydroxyl compound, and further preferably an active ester compound obtained by a carboxylic acid compound and a phenol compound and / or a naphthol compound. Moreover, it is further preferred that an aromatic compound having two or more active ester groups in one molecule is obtained by a reactant of a carboxylic acid compound and an aromatic compound having a phenolic hydroxyl group. Moreover, the active ester curing agent is particularly preferably an aromatic compound obtained by a reactant of a compound having at least two or more carboxylic acids in one molecule and an aromatic compound having a phenolic hydroxyl group, and an aromatic compound having two or more active ester groups in one molecule of the aromatic compound. In addition, the active ester compound can be linear or branched. In addition, the compound having at least two carboxylic acids in one molecule can improve compatibility with the resin composition if it is a compound containing an aliphatic chain, and can improve heat resistance if it is a compound having an aromatic ring. The active ester curing agent can be used alone or in combination of two or more.

[0056] Examples of usable carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Among them, from the viewpoint of improving heat resistance when used as a cured product, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, and isophthalic acid and terephthalic acid are more preferred. Examples of thiocarboxylic acid compounds include thioacetic acid and thiobenzoic acid.

[0057] Specific examples of phenolic compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene-type biphenol compounds (polycyclopentadiene-type biphenol compounds), phenol novolac resins, and the like.

[0058] Among them, from the viewpoint of improving heat resistance and solubility when used as a cured product, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyroglucinol, dicyclopentadiene-type biphenol compounds (polycyclopentadiene-type biphenol compounds), and phenol novolac resins are preferred, and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyroglucinol, dicyclopentadiene-type biphenol compounds (polycyclopentadiene-type biphenol compounds), and phenol novolac resins are more preferred. Compounds), phenol novolac resins, more preferably 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene type biphenol compounds (polycyclopentadiene type biphenol compounds), phenol novolac resins, further preferably 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type biphenol compounds (polycyclopentadiene type biphenol compounds), phenol novolac resins, more preferably 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type biphenol compounds (polycyclopentadiene type biphenol compounds), particularly preferably dicyclopentadiene type biphenol compounds (polycyclopentadiene type biphenol compounds). As examples of thiol compounds, specifically benzenedithiol, triazinedithiol, etc. can be cited.

[0059] More specifically, the active ester curing agent containing a dicyclopentadiene-type biphenol condensation structure includes a compound represented by the following formula (1).

[0060]

[0061] In the formula (1), the two Rs are independently phenyl or naphthyl. k represents 0 or 1. n is 0.05 to 2.5 as an average value of the repeating units.

[0062] From the viewpoint of reducing the dielectric loss tangent and improving the heat resistance, R is preferably a naphthyl group. k is preferably 0. Furthermore, n is preferably 0.25 to 1.5.

[0063] As the active ester curing agent, the active ester compounds disclosed in Japanese Patent Laid-Open No. 2004-277460 can be used, and commercially available active ester curing agents can also be used. As examples of commercially available active ester curing agents, specifically preferably active ester curing agents containing dicyclopentadiene type biphenol condensation structure, active ester curing agents containing naphthalene structure, active ester curing agents containing acetylated products of phenol novolac resin, active ester curing agents containing benzoylated products of phenol novolac resin, wherein more preferably active ester curing agents containing naphthalene structure, active ester curing agents containing dicyclopentadiene type biphenol compound (polycyclopentadiene type biphenol compound) structure. Examples of active ester curing agents containing a dicyclopentadiene-type biphenol compound (polycyclopentadiene-type biphenol compound) structure include EXB9451, EXB9460, EXB9460S, and HPC8000-65T (manufactured by DIC Corporation), examples of active ester curing agents containing a naphthalene structure include EXB9416-70BK (manufactured by DIC Corporation), examples of active ester curing agents containing an acetylated product of a phenol novolac resin include DC808 (manufactured by Mitsubishi Chemical Corporation), and examples of active ester curing agents containing a benzoylated product of a phenol novolac resin include YLH1026 (manufactured by Mitsubishi Chemical Corporation). HPC8000-65T (an active ester curing agent containing a dicyclopentadiene-type biphenol compound (polycyclopentadiene-type biphenol compound) structure) manufactured by DIC Corporation is particularly preferred.

[0064] -Cyanate Curing Agent-

[0065] The cyanate curing agent used in the photosensitive resin composition of the present invention can improve the heat resistance, dielectric properties, and water resistance of the cured product, and is particularly excellent in heat resistance. There are no particular restrictions on the cyanate curing agent, and examples thereof include phenolic (phenolic phenolic type, alkylphenolic phenolic type, etc.) cyanate curing agents, dicyclopentadiene type cyanate curing agents, bisphenol type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate curing agents, and prepolymers obtained by triazinization of a portion thereof. The weight average molecular weight of the cyanate curing agent is not particularly limited, but is preferably 500 to 4500, and more preferably 600 to 3000. Specific examples of cyanate curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylene))benzene, bis(4-cyanatephenyl)sulfide, and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolac resins, cresol novolac resins, and phenolic resins containing a dicyclopentadiene structure, and prepolymers obtained by triazinizing a portion of these cyanate resins. These may be used alone or in combination of two or more. Examples of commercially available cyanate resins include phenol novolac type multifunctional cyanate resins (PT30S manufactured by Lonza Japan Co., Ltd.), prepolymers in which a part or all of bisphenol A dicyanate is triazinated to become a trimer (BA230S75 manufactured by Lonza Japan Co., Ltd.), and dicyclopentadiene structure-containing cyanate resins (DT-4000 and DT-7000 manufactured by Lonza Japan Co., Ltd.). Particularly preferred are "PT30S" (phenol novolac type multifunctional cyanate resin) and "BA230S75" (a part or all of bisphenol A dicyanate is triazinated to become a trimer) manufactured by Lonza Japan Co., Ltd.

[0066] -Benzoxazine curing agent-

[0067] The benzoxazine curing agent used in the photosensitive resin composition of the present invention can improve the heat resistance, dielectric properties, and water resistance of the cured product. The benzoxazine curing agent is not particularly limited, and specific examples thereof include Fa-type benzoxazine, Pd-type benzoxazine (manufactured by Shikoku Chemicals Co., Ltd.), and HFB2006M (manufactured by Showa High Molecular Co., Ltd.), and Pd-type benzoxazine (manufactured by Shikoku Chemicals Co., Ltd.) is particularly preferred.

[0068] The active ester curing agent, the cyanate curing agent, and the benzoxazine curing agent as component (B) may be used alone or in combination of two or more. Active ester curing agents are particularly preferred from the viewpoint of reducing dielectric loss factor and water absorption.

[0069] When the nonvolatile matter of the photosensitive resin composition is 100 mass %, the content of the component (B) is preferably 1 to 30 mass %, more preferably 3 to 25 mass %, and even more preferably 5 to 20 mass %.

[0070] <(C) Ingredients>

[0071] (C) Component is a compound having a (meth)acrylate structure.

[0072] The compound having a (meth)acrylate structure is not limited to the following compounds, and examples thereof include: hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; mono- or di-acrylates of glycols such as ethylene glycol, methoxytetraglycol, polyethylene glycol, and propylene glycol; acrylamides such as N,N-dimethylacrylamide and N-hydroxymethylacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate; polyacrylates of polyhydric alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol, or adducts of these with ethylene oxide, propylene oxide, or ε-caprolactone; acrylates of phenols such as phenoxy acrylate and phenoxyethyl acrylate, or adducts of these with ethylene oxide or propylene oxide; epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether; melamine acrylates; and / or methacrylates corresponding to the above acrylates. Among them, polyvalent acrylates or polyvalent methacrylates are preferred. For example, as trivalent acrylates or methacrylates, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane EO addition tri(meth)acrylate, glycerol PO addition tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetrafurfuryl alcohol oligo(meth)acrylate, ethyl carbitol oligo(meth)acrylate, 1,4-butanediol oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, N,N,N',N'-tetra(β-hydroxyethyl)ethylenediamine (meth)acrylate, etc. can be cited. Examples of acrylates or methacrylates having a valence of 3 or more include phosphate triester (meth)acrylates such as tris(2-(meth)acryloyloxyethyl)phosphate, tris(2-(meth)acryloyloxypropyl)phosphate, tris(3-(meth)acryloyloxypropyl)phosphate, tris(3-(meth)acryloyl-2-hydroxyoxypropyl)phosphate, di(3-(meth)acryloyl-2-hydroxyoxypropyl)(2-(meth)acryloyloxyethyl)phosphate, and (3-(meth)acryloyl-2-hydroxyoxypropyl)di(2-(meth)acryloyloxyethyl)phosphate. From the viewpoint of improving the crosslinking property of the cured product and improving water resistance and heat resistance, component (C) preferably has an epoxy group. Particularly preferred are the "acrylate compound having a cresol novolac resin structure and an epoxy group" synthesized in Synthesis Example 1 and the "methacrylate compound having a dixylenol structure, a biscresol fluorene structure and an epoxy group" synthesized in Synthesis Example 2. These (meth)acrylate compounds may be used alone or in combination of two or more.

[0073] From the viewpoint of improving the clarity, the component (C) preferably contains a polymer having a (meth)acrylate structure having a weight average molecular weight of 500 to 100,000, more preferably 700 to 70,000, further preferably 1,000 to 50,000, and particularly preferably 1,500 to 35,000.

[0074] It should be noted that the weight average molecular weight in the present invention can be measured by gel permeation chromatography (GPC) (polystyrene conversion). The weight average molecular weight measured by the GPC method can be specifically measured using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko (Strain) as a column, chloroform as a mobile phase, etc., measured at a column temperature of 40°C, and calculated using a standard curve of standard polystyrene.

[0075] In the photosensitive resin composition of the present invention, in order to improve the insulation reliability, as the component (C), a compound having no carboxyl group is preferably used, but the compound may have a carboxyl group to the extent that the insulation reliability of the photosensitive resin composition of the present invention is not impaired. For example, the acid value of the component (C) is preferably 20 mgKOH / g or less, more preferably 10 mgKOH / g or less, further preferably 5 mgKOH / g or less, further preferably 3 mgKOH / g or less, and particularly preferably 1 mgKOH / g or less.

[0076] When the nonvolatile matter of the photosensitive resin composition is 100 mass %, the content of the component (C) is preferably 1 to 25 mass %, more preferably 5 to 15 mass %.

[0077] The photosensitive resin composition of the present invention may further contain the following components.

[0078] <(D) Photopolymerization initiator>

[0079] The photosensitive resin composition of the present invention further contains (D) a photopolymerization initiator, so that the resin composition can be effectively photocured to form a cured product. (D) The photopolymerization initiator is not particularly limited, and examples thereof include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-[4-(4-morpholino)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, benzophenone, methyl benzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl-(2,4 Alkyl phenone-based photopolymerization initiators such as alkyl phenones, bis(2,4,6-trimethylbenzoyl)phenylphosphinate, 4,4'-bis(diethylamino)benzophenone, 1-hydroxycyclohexylbenzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one; acyl phosphine oxide-based photopolymerization initiators such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; oxime ester-based photopolymerization initiators such as 1,2-octanedione and 1-[4-(phenylthio)-,2-(O-benzoyloxime)]; sulfonium salt-based photopolymerization initiators, etc. In particular, acylphosphine oxide-based photopolymerization initiators such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by BASF Japan, IC819) and oxime ester-based photopolymerization initiators such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)] (manufactured by BASF Japan, OXE-01) are preferred because they are highly sensitive. The photopolymerization initiator may be used alone or in combination of two or more.

[0080] The amount of the photopolymerization initiator (D) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.3% by mass or more, based on 100% by mass of the nonvolatile component in the photosensitive resin composition, from the viewpoint of sufficiently photocuring the photosensitive resin composition and improving insulation reliability. On the other hand, the amount of the photopolymerization initiator is preferably 2% by mass or less, more preferably 1% by mass or less, and further preferably 0.5% by mass or less, based on 100% by mass of the nonvolatile component in the photosensitive resin composition, from the viewpoint of preventing a decrease in dimensional stability due to excessive sensitivity.

[0081] <(E) Inorganic fillers>

[0082] The photosensitive resin composition of the present invention can reduce the thermal expansion coefficient by further containing (E) inorganic filler. As (E) inorganic filler, for example, silica, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, etc., among which amorphous silica, fused silica, hollow silica, crystalline silica, synthetic silica and other silica are particularly suitable. As silica, spherical silica is preferred. They can be used alone or in combination of two or more. As commercially available preferred spherical fused silica, for example, "SOC2" and "SOC1" manufactured by Admatex can be cited.

[0083] From the perspective of improving insulation reliability and photocurability, the average particle size of the (E) inorganic filler is preferably less than 1 μm, more preferably less than 0.8 μm, further preferably less than 0.6 μm, and further preferably less than 0.4 μm. On the other hand, from the perspective of preventing agglomeration of the inorganic filler, the average particle size of the (E) inorganic filler is preferably more than 0.01 μm, more preferably more than 0.05 μm. It should be noted that as an inorganic filler, in order to improve moisture resistance and dispersibility, it is preferred to use a silane coupling agent (epoxy silane coupling agent, amino silane coupling agent, mercapto silane coupling agent, etc.), a titanate coupling agent, a silazane compound and other surface treatment agents for surface treatment of inorganic fillers. They can be used in one or in combination of two or more.

[0084] Examples of epoxysilane coupling agents include glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.; examples of aminosilane coupling agents include aminopropylmethoxysilane, aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2(aminoethyl)aminopropyltrimethoxysilane, etc.; examples of mercaptosilane coupling agents include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, etc. These can be used alone or in combination of two or more. Examples of commercially available coupling agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0085] Examples of titanate coupling agents include butyl titanate dimer, octanediol titanium, bis(triethanolamine)diisopropoxytitanium, dihydroxytitanium dilactate, dihydroxydi(ammonium lactate)titanium, bis(dioctyl pyrophosphate)ethylene glycol titanate, bis(dioctyl pyrophosphate)hydroxyacetic acid titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra(2-ethylhexyl) titanate, tetraisopropyl bis(dioctyl phosphite)titanate, tetraoctyl bis(ditridecyl phosphite)titanate, bis( The invention also includes tetrakis(2,2-diallyloxymethyl-1-butyl)titanate, trioctanoyl isopropyl titanate, tricumylbenzene isopropyl titanate, triisostearoyl isopropyl titanate, isostearyldiacryl isopropyl titanate, dimethacryloyl isostearyl titanate, tri(dioctyl phosphate) isopropyl titanate, tri(dodecylbenzenesulfonyl) isopropyl titanate, tri(dioctyl pyrophosphate) isopropyl titanate, tri(N-amidoethyl-aminoethyl) isopropyl titanate, etc. These can be used alone or in combination of two or more.

[0086] Examples of the silazane compound include hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, octamethyltrisilazane, hexa(tert-butyl)disilazane, hexabutyldisilazane, hexaoctyldisilazane, 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, hexaphenyldisilazane, dimethylaminotrimethylsilazane, trisilazane, cyclotrisilazane, and 1,1,3,3,5,5-hexamethylcyclotrisilazane. Hexamethyldisilazane is particularly preferred. These can be used alone or in combination of two or more.

[0087] For (E) inorganic filler, from the viewpoint of improving the dispersibility of the photosensitive resin composition, it is preferred to use an inorganic filler surface-treated with a silazane compound. Moreover, after surface treatment with a silazane compound, by surface treatment with a silane coupling agent, the improvement of dispersibility can be further achieved. The amount of the silazane compound used in the surface treatment is preferably 0.001% to 0.3% by mass relative to 100% by mass of the inorganic filler, and more preferably 0.005% to 0.2% by mass. As a spherical fused silica surface-treated with hexamethyldisilazane, for example, "SC2050" made by (strain) Adomatex can be cited. In addition, the amount of the silane coupling agent used in the surface treatment is preferably 0.1% to 6% by mass relative to 100% by mass of the inorganic filler, more preferably 0.2% to 4% by mass, and further preferably 0.3% to 3% by mass.

[0088] (E) The average particle size of the inorganic filler can be measured by a laser diffraction-scattering method based on Mie scattering theory. Specifically, a laser diffraction scattering particle size distribution measuring device can be used to make the particle size distribution of the inorganic filler on a volume basis, and the median particle size is measured as the average particle size. The sample can preferably be a sample in which the inorganic filler is dispersed in water using ultrasound. As a laser diffraction scattering particle size distribution measuring device, LA-500, LA-750, etc. manufactured by (strain) Horiba Manufacturing can be used.

[0089] From the viewpoint of reducing the coefficient of linear thermal expansion of the cured product and preventing deformation of the cured product, when the non-volatile component in the photosensitive resin composition is set to 100% by mass, the content of the inorganic filler (E) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and further preferably 40% by mass or more. From the viewpoint of improving heat resistance, it is particularly preferably 50% by mass or more. On the other hand, from the viewpoint of preventing the decrease of alkali developability and improving photocurability, when the non-volatile component in the photosensitive resin composition is set to 100% by mass, the content of the inorganic filler (E) is preferably 85% by mass or less, more preferably 75% by mass or less, and further preferably 65% ​​by mass or less.

[0090] <(F) Curing accelerator>

[0091] The photosensitive resin composition of the present invention further contains (F) a curing accelerator, whereby the heat resistance, adhesiveness, chemical resistance and the like of the cured product can be improved.

[0092] (F) The curing accelerator is not particularly limited, and examples thereof include amine curing accelerators, guanidine curing accelerators, imidazole curing accelerators, phosphonium curing accelerators, and metal curing accelerators, etc. These may be used alone or in combination of two or more.

[0093] The amine-based curing accelerator is not particularly limited, and examples thereof include trialkylamines such as triethylamine and tributylamine, amine compounds such as 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5.4.0)-undecene, etc. These can be used alone or in combination of two or more.

[0094] The guanidine curing accelerator is not particularly limited, and examples thereof include cyanoguanidine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide. These may be used alone or in combination of two or more.

[0095] The imidazole curing accelerator is not particularly limited, and examples thereof include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine. , 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds and epoxy resins. These can be used alone or in combination of two or more.

[0096] The phosphonium curing accelerator is not particularly limited, and examples thereof include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc. These may be used alone or in combination of two or more.

[0097] In the photosensitive resin composition of the present invention, as a curing accelerator (except a metal curing accelerator), an amine curing accelerator or an imidazole curing accelerator is preferably used, and 4-dimethylaminopyridine and 2-phenyl-4-methylimidazole are particularly preferably used. When the non-volatile component in the photosensitive resin composition is set to 100% by mass, the content of the curing accelerator (except a metal curing accelerator) is preferably in the range of 0.005% by mass to 1% by mass, and more preferably in the range of 0.01% by mass to 0.08% by mass. If it is less than 0.005% by mass, the curing becomes slow and there is a tendency to require a longer curing time. If it exceeds 1% by mass, there is a tendency for the storage stability of the resin composition to decrease.

[0098] As a metal curing accelerator, it is not particularly limited, for example, organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin can be listed. As a specific example of an organic metal complex, organic cobalt complexes such as cobalt acetylacetonate (II), cobalt acetylacetonate (III), organic copper complexes such as copper acetylacetonate (II), organic zinc complexes such as zinc acetylacetonate (II), organic iron complexes such as iron acetylacetonate (III), organic nickel complexes such as nickel acetylacetonate (II), and organic manganese complexes such as manganese acetylacetonate (II) can be listed. As an organic metal salt, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc. can be listed. They can be used in one or in combination of two or more.

[0099] In the photosensitive resin composition of the present invention, as a metal curing accelerator, an organic cobalt complex is preferably used, and cobalt (III) acetylacetonate is particularly preferably used. Regarding the content of the metal curing accelerator, when the total solid content of the photosensitive resin composition is set to 100% by mass, the content of the metal based on the metal curing catalyst is preferably in the range of 25ppm to 500ppm, and more preferably in the range of 30ppm to 200ppm.

[0100] <(G) Organic fillers>

[0101] The photosensitive resin composition of the present invention can relax the stress of the cured product and prevent cracks from occurring in the cured product by further containing (G) an organic filler. Examples of the (G) organic filler include rubber particles, polyamide microparticles, and silicone particles. In the present invention, rubber particles are preferably used.

[0102] As the rubber particles, any rubber particles may be used as long as they are microparticles of a resin that is chemically crosslinked to exhibit rubber elasticity and is insoluble and infusible in an organic solvent, and examples thereof include acrylonitrile butadiene rubber particles, butadiene rubber particles, and acrylic rubber particles. As the rubber particles, specifically, XER-91 (manufactured by Japan Synthetic Rubber Co., Ltd.), Stafyloid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (manufactured by GANTSU KASEI CO., LTD.), Paralleloid EXL2655, EXL2602 (manufactured by Kureha Chemical Co., Ltd.), and the like are preferably AC3816N (manufactured by GANTSU KASEI CO., LTD.).

[0103] As polyamide microparticles, any polyamide microparticles may be used as long as they are microparticles of 50 μm or less of a resin having an amide bond, and examples thereof include aliphatic polyamides such as nylon, aromatic polyamides such as Kevlar, polyamide-imide, etc. As polyamide microparticles, specifically, VESTOSINT 2070 (manufactured by Dicel Hyrule Co., Ltd.) and SP500 (manufactured by Toray Industries, Ltd.) may be mentioned.

[0104] (G) The average particle size of the organic filler is preferably in the range of 0.005 μm to 1 μm, and more preferably in the range of 0.2 μm to 0.6 μm. (G) The average particle size of the organic filler can be measured by dynamic light scattering. (G) The average particle size of the organic filler can be measured, for example, as follows: the organic filler is uniformly dispersed in an appropriate organic solvent by ultrasound, etc., and a particle size distribution of the organic filler is prepared based on mass using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.), and the median particle size is taken as the average particle size.

[0105] From the viewpoint of improving heat resistance and laser processability, the content of the (G) organic filler is preferably 0.1 to 6% by mass, more preferably 0.5 to 4% by mass, based on 100% by mass of the total solid content of the photosensitive resin composition.

[0106] <(H) Photosensitizer>

[0107] In the photosensitive resin composition of the present invention, as (H) photosensitizer, tertiary amines such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isopentyl ester, amyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. can be added, and photosensitizers such as pyrazoline (ピラリゾン), anthracene, coumarins, xanthone, thioxanthone, etc. can also be added. In the present invention, as a photosensitizer, thioxanthones are preferably used, and 2,4-diethylthioxanthone is more preferably used. The photosensitizer can be used alone or in combination of two or more.

[0108] <(I) Organic solvent>

[0109] The photosensitive resin composition of the present invention may further contain (I) an organic solvent to adjust the varnish viscosity. As (I) organic solvent, for example, ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, aliphatic hydrocarbons such as octane and decane, petroleum ether, naphtha, hydrogenated naphtha, solvent oil, and other petroleum solvents, etc., among which solvent oil and methyl ethyl ketone are preferred. These can be used alone or in combination of two or more. The content of the organic solvent when used can be appropriately adjusted from the perspective of the coating property of the photosensitive resin composition.

[0110] <(J) Other additives>

[0111] (J) Other additives include, for example, fine particles of melamine, organic bentonite, etc., colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, thickeners such as bentonite and montmorillonite, silicone-based, fluorine-based, and vinyl resin-based defoamers, brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus compounds, aromatic condensed phosphates, halogen-containing condensed phosphates, and other flame retardants, and thermosetting resins such as phenolic curing agents.

[0112] The photosensitive resin composition of the present invention can be produced as follows: the above (A) to (C) (and any (D) to (J)) are appropriately mixed, and kneaded or stirred as needed using a kneading device such as a three-roll mill, a ball mill, a beads mill, a sand mill, or a stirring device such as a high-speed mixer or a planetary mixer, thereby producing a resin varnish.

[0113] The use of the photosensitive resin composition of the present invention is not particularly limited, and can be used for a wide range of uses requiring a resin composition, such as photosensitive films, photosensitive films with supports, insulating resin sheets such as prepregs, circuit substrates (laminated board uses, multilayer printed wiring board uses, etc.), solder resists, underfill materials, die bonding materials, semiconductor sealing materials, hole-filling resins, and component embedding resins. Among them, it can be preferably used as a resin composition for an insulating layer of a multilayer printed wiring board (a multilayer printed wiring board using a cured product of a photosensitive resin composition as an insulating layer), and can be particularly preferably used as a resin composition for an interlayer insulating layer (a multilayer printed wiring board using a cured product of a photosensitive resin composition as an interlayer insulating layer), and a resin composition for plating formation (a multilayer printed wiring board having a plating layer formed on a cured product of a photosensitive resin composition).

[0114] <Photosensitive film>

[0115] The photosensitive resin composition of the present invention is applied to a supporting substrate in a resin varnish state, and the organic solvent is dried to form a resin composition layer, thereby obtaining a photosensitive film. In addition, the photosensitive film pre-formed on the support can be laminated on the supporting substrate for use. The photosensitive film of the present invention can be laminated on various supporting substrates. As the supporting substrate, substrates such as glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates can be mainly listed.

[0116] <Photosensitive film with support>

[0117] The photosensitive resin composition of the present invention can be suitably used in the form of a photosensitive film with a support having a resin composition layer formed on a support. That is, the photosensitive film with a support is a layer of the photosensitive resin composition formed on a support. Examples of the support include polyethylene terephthalate film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, triacetoacetate film, and the like, and polyethylene terephthalate film is particularly preferred.

[0118] As commercially available supports, for example, polypropylene films such as "Alfan MA-410" and "E-200C" manufactured by Prince Paper Co., Ltd., polypropylene films such as Shin-Etsu Film Co., Ltd., and PS series polyethylene terephthalate films such as "PS-25" manufactured by Teijin Limited, etc. can be cited, but are not limited to these. For these supports, in order to facilitate the removal of the resin composition layer, a release agent such as a silicone coating agent can be applied to the surface. The thickness of the support is preferably in the range of 5μm to 50μm, and more preferably in the range of 10μm to 25μm. When the thickness is less than 5μm, there is a tendency for the support (support film) to break easily when the support is peeled off before development. On the other hand, if the thickness exceeds 50μm, there is a tendency for the resolution to decrease when exposure is performed from the support. In addition, a support with a low white point (fish eye) is preferred. Here, white spots are caused by foreign matter, undissolved matter, oxidative degradation products, etc. of the material entering the film when the material is hot-melted and the film is produced by kneading, extrusion, biaxial stretching, casting, etc.

[0119] In addition, in order to reduce the scattering of light when exposed to active energy rays such as ultraviolet rays, the support is preferably a support with excellent transparency. Specifically, the support is preferably a support with a turbidity (haze standardized by JIS-K6714) of 0.1 to 5 as a transparency index. Furthermore, the resin composition layer can be protected by a protective film.

[0120] The resin composition layer side of the photosensitive film with a support is protected with a protective film, thereby preventing the adhesion or scratches of dust on the surface of the resin composition layer. As a protective film, a film made of the same material as the above-mentioned support can be used. The thickness of the protective film is not particularly limited, preferably in the range of 1μm to 40μm, more preferably in the range of 5μm to 30μm, and further preferably in the range of 10μm to 30μm. When the thickness is less than 1μm, the operability of the protective film tends to decrease, and if it exceeds 40μm, there is a tendency for the cheapness to deteriorate. It should be noted that the preferred protective film is that the adhesion between the resin composition layer and the protective film is smaller than the adhesion between the resin composition layer and the support.

[0121] The photosensitive film with support of the present invention can be prepared according to a method known to those skilled in the art, for example, a resin varnish is prepared by dissolving the photosensitive resin composition of the present invention in an organic solvent, the resin varnish is applied on the support, and the organic solvent is dried by heating or blowing hot air to form a resin composition layer, thereby manufacturing the photosensitive film with support of the present invention. Specifically, after completely removing the bubbles in the photosensitive resin composition by vacuum defoaming method, the photosensitive resin composition is applied on the support, the solvent is removed by a hot air furnace or a far infrared furnace, and it is dried, and then a protective film is laminated on the resin composition layer as needed to manufacture the photosensitive film with support. The specific drying conditions vary depending on the curability of the resin composition and the amount of organic solvent in the resin varnish, but in a resin varnish containing 30% to 60% by mass of organic solvent, it can be dried at 80°C to 120°C for 3 minutes to 13 minutes. From the perspective of preventing the diffusion of organic solvents in subsequent processes, the amount of residual organic solvent in the resin composition layer is preferably 5% by mass or less, and more preferably 2% by mass or less relative to the total amount of the resin composition layer. Those skilled in the art can set appropriate and suitable drying conditions through simple experiments. From the viewpoint of improving operability and preventing the sensitivity and resolution inside the resin composition layer from decreasing, the thickness of the resin composition layer is preferably in the range of 5 μm to 500 μm, more preferably in the range of 10 μm to 200 μm, further preferably in the range of 15 μm to 150 μm, further preferably in the range of 20 μm to 100 μm, and particularly preferably in the range of 20 μm to 60 μm.

[0122] Examples of a coating method for the photosensitive resin composition include a gravure coating method, a micro gravure coating method, a reverse coating method, a kiss reverse coating method, a die coating method, a slot die method, a lip coating method, a comma coating method, a blade coating method, a roll coating method, a knife coating method, a curtain coating method, a chamber gravure coating method, a slot orifice method, a spray coating method, and a dip coating method.

[0123] The photosensitive resin composition can be applied in several times or once, and can also be applied in a combination of different methods. Among them, the die coating method with excellent uniform coating properties is preferred. In addition, in order to avoid the mixing of foreign matter, it is preferred to implement the coating process in an environment where less foreign matter is generated, such as a clean room.

[0124] <Multilayer printed circuit board>

[0125] Next, an example in which a multilayer printed wiring board is produced using the photosensitive resin composition will be described.

[0126] When the photosensitive resin composition of the present invention is used to produce an interlayer insulating layer, the following advantages can be obtained: (1) through-hole opening can be performed in batches; and (2) an interlayer insulating layer having a through-hole position accuracy superior to that obtained by laser opening can be obtained.

[0127] (Coating and drying process)

[0128] The photosensitive resin composition is directly coated on the circuit substrate in the state of resin varnish, and the organic solvent is dried to form a photosensitive film on the circuit substrate. As the circuit substrate, for example, glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate, etc. can be cited. It should be noted that the circuit substrate here refers to a substrate having a conductor layer (circuit) processed by patterning formed on one or both sides of the above-mentioned substrate. In addition, in a multilayer printed wiring board formed by alternately stacking a conductor layer and an insulating layer, a substrate having a conductor layer (circuit) processed by patterning formed on one or both sides of the outermost layer of the multilayer printed wiring board is also included in the circuit substrate mentioned here. It should be noted that a roughening treatment can be pre-implanted on the surface of the conductor layer by blackening treatment, copper etching, etc.

[0129] As a coating method, full-surface printing using a screen printing method is usually used, but in addition, any coating method that can be evenly coated can be used. For example, a spray coating method, a hot melt coating method, a scraper coating method, an applicator method, a scraper coating method, a blade coating method, an air knife coating method, a curtain flow coating method, a roller coating method, a gravure coating method, an offset printing method, a dip coating method, a brush coating, and other conventional coating methods can be used. After coating, it is dried with a hot air furnace or a far infrared furnace as needed. The drying conditions are preferably 3 minutes to 13 minutes at 80°C to 120°C. In this way, a photosensitive film can be formed on the circuit substrate.

[0130] (Lamination process)

[0131] In addition, when a photosensitive film with a support is used, the resin composition layer is laminated on one or both sides of the circuit substrate using a vacuum laminator. In the lamination process, when the photosensitive film with a support has a protective film, after removing the protective film, the photosensitive film and the circuit substrate are preheated as needed, and the resin composition layer is pressed and heated while being bonded to the circuit substrate. The photosensitive film of the present invention is suitable for laminating on the circuit substrate under reduced pressure using a vacuum lamination method.

[0132] The conditions of the lamination step are not particularly limited. For example, the pressing temperature (lamination temperature) is preferably 70° C. to 140° C., and the pressing pressure is preferably 1 kgf / cm 2 ~11kgf / cm 2 (9.8×10 4 N / m 2 ~107.9×10 4 N / m 2 ), the pressing time is preferably 5 seconds to 300 seconds, and the lamination is preferably carried out under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. In addition, the lamination process can be a batch type or a continuous type using a roller. The vacuum lamination method can be carried out using a commercially available vacuum laminator. As commercially available vacuum laminators, for example, a vacuum applicator manufactured by Nichigo Moden Co., Ltd., a vacuum pressurized laminator manufactured by Meiki Seisakusho Co., Ltd., a roller dry coating machine manufactured by Hitachi Industrie Co., Ltd., and a vacuum laminator manufactured by Hitachi Airship Co., Ltd. can be cited. In this way, a photosensitive film can be formed on a circuit substrate.

[0133] (Exposure process)

[0134] After a photosensitive film is provided on the circuit substrate through a coating and drying process or a lamination process, an exposure process is performed to irradiate a predetermined portion of the resin composition layer with active light through a mask pattern to photocure the resin composition layer in the irradiated portion. Examples of active light include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferred. The irradiation amount of ultraviolet rays is approximately 10 mJ / cm 2 ~1000mJ / cm 2 The exposure method includes a contact exposure method in which the mask pattern is closely attached to the printed circuit board, and a non-contact exposure method in which parallel light is used for exposure without close attachment. Any of the two methods may be used. In addition, when there is a support on the resin composition layer, the exposure may be performed from the support, or the exposure may be performed after the support is peeled off.

[0135] (Development Process)

[0136] After the exposure step, if a support is present on the resin composition layer, the support is removed, and then wet development or dry development is performed to remove the uncured portion (unexposed portion) and develop, thereby forming a pattern.

[0137] In the case of the wet development, as the developer, a safe, stable and easy-to-operate developer such as an alkaline aqueous solution, an aqueous developer, an organic solvent can be used. In the present invention, the development process using an organic solvent is preferred. In addition, as the developing method, a known method such as spraying, swing dipping, brushing, scraping, etc. can be appropriately used.

[0138] Examples of the organic solvent used as the developer include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropyl alcohol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.

[0139] The concentration of the organic solvent is preferably 2% to 90% by mass relative to the total amount of the developer. In addition, the temperature of the organic solvent can be adjusted according to the developability. Furthermore, the organic solvent can be used alone or in combination of two or more. As an organic solvent-based developer used alone, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone, propylene glycol 1-monomethyl ether 2-acetate (PGMEA) can be listed. In the present invention, PGMEA is preferred.

[0140] In the pattern formation of the present invention, two or more of the above-mentioned developing methods may be used in combination as needed. The developing methods include a dip method, a puddle method, a spray method, a high-pressure spray method, a brush, and slapping. In order to improve the resolution, a high-pressure spray method is preferred. When the spray method is used, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

[0141] (Postbake process)

[0142] After the development process is completed, a hardening process is performed to form an insulating layer (cured product). Examples of the hardening process include ultraviolet irradiation using a high-pressure mercury lamp and a heating process using a clean oven. The amount of ultraviolet irradiation can be adjusted as needed, for example, 0.05 J / cm 2 ~10J / cm 2In addition, the heating conditions can be appropriately selected according to the type and content of the resin component in the resin composition, preferably within the range of 150°C to 220°C for 20 minutes to 180 minutes, and more preferably within the range of 160°C to 200°C for 30 minutes to 120 minutes.

[0143] (Plating process)

[0144] Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As dry plating, known methods such as evaporation, sputtering, and ion plating can be used. The evaporation method (vacuum evaporation method) can be, for example, by placing a support in a vacuum container and heating and evaporating the metal, thereby forming a metal film on the insulating layer. The sputtering method can also be, for example, by placing a support in a vacuum container, introducing an inert gas such as argon, applying a DC voltage, and bombarding the target metal with the ionized inert gas, and forming a metal film on the insulating layer by the sputtered metal.

[0145] In the case of wet plating, the surface of the formed insulating layer is sequentially subjected to swelling treatment using a swelling liquid, roughening treatment using an oxidant, and neutralization treatment using a neutralizing liquid, thereby forming a concave and convex anchor. The swelling treatment using the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50° C. to 80° C. for 5 to 20 minutes. Examples of the swelling liquid include alkaline solutions, and examples of the alkaline solution include sodium hydroxide solutions, potassium hydroxide solutions, and the like. As commercially available swelling liquid, for example, Swerling Dip Security P (Swelling Dip Security P) and Swerling Dip Security SBU (Swelling Dip Security SBU) manufactured by Attech Japan Co., Ltd. can be cited. The roughening treatment using an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60° C. to 80° C. for 10 to 30 minutes. As an oxidizing agent, for example, an alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, etc. can be cited. In addition, the permanganate concentration in the alkaline permanganate solution is preferably 5% to 10% by weight. As commercially available oxidants, for example, alkaline permanganate solutions such as Concentrator Conpack CP and Dextrin Sodium Securin P manufactured by Attech Japan Co., Ltd. can be cited. The neutralization treatment using the neutralizing solution is performed by immersing in the neutralizing solution at 30°C to 50°C for 3 minutes to 10 minutes. As a neutralizing liquid, an acidic aqueous solution is preferable, and a commercially available product includes Riptron P manufactured by Atotron Co., Ltd.

[0146] Next, the conductor layer is formed by combining electroless plating and electrolytic plating. In addition, a protective plating layer having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a method for subsequent pattern formation, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.

[0147] <Semiconductor devices>

[0148] A semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention. A semiconductor device can be manufactured by installing a semiconductor chip in the conductive part of the multilayer printed wiring board of the present invention. "Conductive part" means "a part that conducts electrical signals in a multilayer printed wiring board", and its position can be either the surface or the buried part. In addition, the semiconductor chip is not particularly limited as long as it is a circuit element made of semiconductor.

[0149] The method for mounting the semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip can function effectively. Specifically, there can be listed a wire bonding mounting method, a flip chip mounting method, a mounting method using a built-in non-bump layer (ball-type bump layer, BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), etc.

[0150] The photosensitive resin composition of the present invention can provide a resin composition having photosensitivity and excellent insulation reliability, and having physical properties suitable for stacking layers of a multilayer printed wiring board. Furthermore, it can provide a cured product having excellent dielectric properties, water resistance, and heat resistance, and suitable for development in an organic solvent. These properties are described in detail below.

[0151] The dielectric loss factor of the cured product of the photosensitive resin composition of the present invention can be measured by the <Determination of Dielectric Properties> described later. The dielectric loss factor can be specifically measured by the cavity resonator perturbation method, with the frequency set to 5.8 GHz and the measurement temperature set to 23°C. From the viewpoint of preventing heat generation at high frequencies, reducing signal delays and signal noise, the dielectric loss factor is preferably 0.05 or less, more preferably 0.04 or less, further preferably 0.03 or less, further preferably 0.02 or less, and particularly preferably 0.013 or less. On the other hand, the lower limit of the dielectric loss factor is not particularly limited, and is 0.005 or more.

[0152] The water resistance (water absorption) of the cured product of the photosensitive resin composition of the present invention can be measured by the measurement method described in the <Measurement of Water Resistance> described later. From the viewpoint of preventing voids from being generated during the production of a printed wiring board and improving insulation reliability, the water absorption is preferably 3% or less, more preferably 2% or less, further preferably 1% or less, and further preferably 0.8% or less. On the other hand, the lower limit of the water absorption is not particularly limited, and is 0.01% or more, 0.1% or more, 0.2% or more, etc.

[0153] The heat resistance of the cured product of the photosensitive resin composition of the present invention can be measured by the measurement method described in the <Evaluation of Heat Resistance> described later. As an indicator of heat resistance, the glass transition temperature can be used from the perspective of preventing the degradation of the cured product when the cured product is given a thermal history. The glass transition temperature is preferably above 110°C. The upper limit of the glass transition temperature is not particularly limited, but is preferably below 300°C. In addition, from the perspective of preventing deformation of the printed wiring board, the thermal expansion coefficient can be used as an indicator of heat resistance. The thermal expansion coefficient is preferably 10 to 30 ppm / °C.

[0154] Example

[0155] The present invention is specifically described below by way of examples, but the present invention is not limited to these examples. It should be noted that "parts" refer to parts by mass.

[0156] <Preparation of evaluation laminate>

[0157] The copper layer of the glass epoxy substrate on which the circuit was formed with a 18 mm thick copper layer was treated with CZ8100 (a surface treatment agent containing an organic acid, manufactured by Meck Co., Ltd.) for roughening. Next, a vacuum laminator (VP160 manufactured by Nichigo Moden Co., Ltd.) was used to laminate the resin composition layer of the photosensitive film with a support obtained in the examples and comparative examples in contact with the surface of the copper circuit, to prepare a laminate in which the glass epoxy substrate, the resin composition layer, and the support were laminated in sequence. The pressing conditions were as follows: after vacuum treatment for 20 seconds, the pressing temperature was 80°C, the pressing pressure was 0.2 MPa, and the pressing time was 20 seconds. The laminate was allowed to stand at room temperature for more than 1 hour, and a circular hole pattern was used on the support of the laminate to form circular holes with a diameter of 80 mm, and a pattern forming device was used with a 100 mJ / cm 2 After standing at room temperature for 30 minutes, the support was peeled off from the laminate. In the embodiment, the entire surface of the resin composition layer on the laminate was immersed in 30°C PGMEA (propylene glycol 1-monomethyl ether 2-acetate) as a developer for development, and then the developer was wiped off and 1 J / cm 2The laminate was irradiated with ultraviolet rays and then heated at 190°C for 60 minutes to form an insulating layer having an opening with a diameter of 80 mm. This was used as an evaluation laminate.

[0158] On the other hand, in the comparative example, the entire surface of the resin composition layer on the laminate was developed by spraying a 1 mass % sodium carbonate aqueous solution at 30° C. as a developer at a spray pressure of 0.15 MPa for 1.5 times the minimum development time (minimum development time for the unexposed portion). 2 The laminate was irradiated with ultraviolet rays and then subjected to a heat treatment at 190° C. for 60 minutes to form an insulating layer having an opening with a diameter of 80 mm.

[0159] <Preparation of Cured Material for Evaluation>

[0160] The resin composition layer of the photosensitive film with support obtained in Examples and Comparative Examples was subjected to a 100 mJ / cm 2 Then, the entire surface of the resin composition layer was exposed to ultraviolet light at 1 J / cm 2 The substrate was irradiated with ultraviolet rays and then heated at 190° C. for 90 minutes to form an insulating layer. The support was then peeled off to prepare a cured product for evaluation.

[0161] <Measurement method, evaluation method>

[0162] First, various measurement methods and evaluation methods are described.

[0163] <Evaluation of photosensitivity>

[0164] (resolution)

[0165] As a definition evaluation, the shape of the resist layer of the circular hole in the laminate was evaluated by SEM observation (magnification 1000 times).

[0166] The following criteria were used for evaluation:

[0167] ○: The round hole shape is good, without curling or peeling;

[0168] ×: The circular hole shape is enlarged by development, and there is curling or peeling.

[0169] (Developability)

[0170] As an evaluation of the developability, the residue at the bottom of the circular holes of the laminate was observed by SEM (magnification 1000 times), and the presence or absence of the residue at the bottom of the circular holes was evaluated according to the following criteria:

[0171] ○: There is no development residue on the substrate with a circular hole of 80 mm in diameter, and the development residue removability is excellent;

[0172] ×: There was development residue on the substrate of the circular hole with a diameter of 80 mm, and the removability of the development residue was poor.

[0173] <Evaluation of insulation reliability>

[0174] On the imide film formed with comb-tooth electrodes (line width (line) / spacing (space) = 15 microns / 15 microns), the resin composition layer of the photosensitive film with a support obtained in the examples and comparative examples was laminated using a vacuum laminator (VP160 manufactured by Nichigo Moden Co., Ltd.). The pressing conditions were vacuum treatment for 20 seconds, a pressing temperature of 80°C, a pressing pressure of 0.2 MPa, and a pressing time of 20 seconds. The laminate was left to stand at room temperature for more than 1 hour, and a pressure of 100 mJ / cm was applied from the support of the laminate. 2 After standing at room temperature for 30 minutes, the support was peeled off from the laminate. Then, 1 J / cm 2 The laminate was irradiated with ultraviolet rays and then heated at 190°C for 60 minutes to be used as an evaluation laminate. The evaluation laminate was placed in a high temperature and high humidity tank at 130°C and 85% humidity, a voltage of 3.3V was applied, and a HAST test was performed in the tank for 100 hours. The insulation resistance value of the evaluation laminate after 100 hours was evaluated according to the following judgment criteria:

[0175] ○:10 8 Ω or more

[0176] ×: 10 8 Ω or less.

[0177] <Measurement of dielectric properties>

[0178] (Dielectric loss factor)

[0179] The evaluation cured product was cut into a piece with a length of 80 mm and a width of 2 mm to prepare an evaluation sample 1. The dielectric loss factor of the evaluation sample 1 was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. using a HP8362B device manufactured by AGILENT TECHNOLOGIES by a cavity resonator perturbation method. The measurement was performed on two evaluation samples 1, and the average value was calculated.

[0180] <Measurement of water resistance>

[0181] (Water absorption)

[0182] The evaluation solidified product was cut into a 5 cm square as the evaluation sample 2. Next, the mass of the evaluation sample 2 was measured, and the evaluation sample after the mass was measured was placed in boiling pure water, and the evaluation sample 2 was left for 1 hour in a state where it was completely immersed. Then, the evaluation sample 2 was taken out, the water on the surface was fully wiped off, and the mass after water absorption was measured to 0.1 mg, and the water resistance WA (%) was calculated using the following formula. The measurement was performed for 4 evaluation samples 2, and the average value was calculated.

[0183] WA=((W1-W0) / W0)×100

[0184] W0: Mass of the evaluation sample before water absorption (g)

[0185] W1: The mass of the evaluation sample after water absorption (g).

[0186] <Evaluation of heat resistance>

[0187] (Glass transition temperature)

[0188] The evaluation cured product was cut into a test piece of 5 mm in width and 15 mm in length as evaluation sample 3. Next, a thermomechanical analysis was performed using a thermomechanical analyzer TMA-SS6100 (manufactured by Seiko Instruments Co., Ltd.) using a tensile load method. After evaluation sample 3 was mounted on the above-mentioned device, it was continuously measured twice under the measurement conditions of a load of 1 g and a heating rate of 5°C / min. For the glass transition temperature, the glass transition temperature (°C) was calculated from the point where the slope of the dimensional change signal in the second measurement changed. For the thermal expansion coefficient, the average linear thermal expansion coefficient (ppm / °C) from 25°C to 150°C in the second measurement was calculated.

[0189] <Synthesis Example 1: Synthesis of an Acrylate Compound Having a Cresol Novolac Resin Structure and an Epoxy Group>

[0190] 2050 g (equivalent weight: 10.0) of cresol novolac epoxy resin [DIC Corporation, EPICLONN-660, epoxy equivalent weight: 205], 360 g of acrylic acid (equivalent weight: 5.0), and 1.5 g of hydroquinone were added to 700 g of diethylene glycol monoethyl ether acetate, and heated and stirred at 90°C to uniformly dissolve. Then, 5.9 g of triphenylphosphine was added, and the temperature was raised to 120°C to react for 12 hours. The obtained reaction solution was diluted with a solvent to obtain an acrylate compound (Product A).

[0191] Epoxy equivalent: 427

[0192] Acid value: 0.49mgKOH / g

[0193] ·Weight average molecular weight: 2000

[0194] A diethylene glycol monoethyl ether acetate solution having a solid content of 65% by mass.

[0195] <Synthesis Example 2: Synthesis of a methacrylate compound having a bixylenol structure, a biscresol fluorene structure and an epoxy group>

[0196] 190 g of bixylenol-type epoxy resin (YX4000 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185), 14 g of bisphenol acetophenone (phenolic hydroxyl equivalent 145), 170 g of biscresol fluorene (manufactured by JFE Chemical Corporation, phenolic hydroxyl equivalent 190), and 150 g of cyclohexanone were added to a reaction container and stirred to dissolve. Then, 0.5 g of tetramethylammonium chloride solution was added dropwise, and the mixture was reacted at 180° C. for 5 hours under a nitrogen atmosphere. Next, the temperature was lowered to 60°C, and a mixed solution of 100 parts of ethyl isocyanate methacrylate (manufactured by Showa Denko K.K., trade name: Karens MOI, methacryloyl equivalent 155) and 0.04 parts of dibutyltin dilaurate was added dropwise through a dropping passage. After the addition was completed, the reaction system was kept at 70°C for 4 hours to eliminate the isocyanate group and obtain a methacrylate compound. After the reaction was completed, the mixture was filtered using a filter cloth and diluted with a solvent to obtain a methacrylate compound (Product B).

[0197] Epoxy equivalent: 6400

[0198] Acid value: 0.73mgKOH / g

[0199] Weight average molecular weight: 29000

[0200] A 1:1 solution of MEK and cyclohexanone having a solid content of 25% by mass.

[0201] <Examples 1 to 3, Comparative Example 1>

[0202] The components were mixed in the proportions shown in Table 1, and three rolls were used for kneading to prepare a resin varnish. Next, the resin varnish was evenly coated on a 16 mm thick polyethylene terephthalate film (R310-16B, manufactured by Mitsubishi Resins Co., Ltd., trade name) using a die coater, and dried to obtain a photosensitive film with a support having a resin composition layer of 20 mm. Drying was performed using a hot air convection dryer at 75 to 120°C (average 100°C) for 4.5 minutes. These measurement results and evaluation results are shown in Table 1.

[0203] [Table 1]

[0204] Table 1

[0205]

[0206] The materials used are as follows,

[0207] (A) Epoxy resin

[0208] HP7200H (DIC Corporation): dicyclopentadiene epoxy resin, epoxy equivalent 280, solvent oil solution containing 65% nonvolatile matter

[0209] HP4032SS (DIC Corporation): liquid naphthalene-based epoxy resin, epoxy equivalent 144

[0210] ·ZX1059 (manufactured by Nippon Steel Chemical Co., Ltd.): 1:1 mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent weight 169

[0211] ·YX4000HK (Mitsubishi Chemical Corporation): crystalline bifunctional epoxy resin, epoxy equivalent 185

[0212] NC3000L (manufactured by Nippon Kayaku Co., Ltd.): biphenyl type epoxy resin, epoxy equivalent 269

[0213] (B) Active ester, cyanate ester, benzoxazine

[0214] HPC8000-65T (manufactured by DIC Corporation): dicyclopentadiene-type biphenol compound (polycyclopentadiene-type biphenol compound) type active ester curing agent, toluene solution with a solid content of 65%

[0215] BA230S75 (manufactured by Lonza Japan Co., Ltd.): prepolymer of bisphenol A dicyanate, cyanate equivalent weight of about 232, MEK solution containing 75% by mass of nonvolatile components

[0216] PT30S (manufactured by Lonza Japan Co., Ltd.): Phenol novolac type multifunctional cyanate ester resin, cyanate ester equivalent of about 133, MEK solution containing 85% by mass of nonvolatile components

[0217] Pd-type benzoxazine (manufactured by Shikoku Chemicals Co., Ltd.): benzoxazine monomer equivalent 217, MEK solution with a nonvolatile content of 60% by mass

[0218] (C) Component: Compound containing (meth)acrylate

[0219] Product A was synthesized according to Synthesis Example 1

[0220] Product B is synthesized according to Synthesis Example 2

[0221] DPHA (manufactured by Nippon Kayaku Co., Ltd.): dipentaerythritol hexaacrylate, acid value 0.5 mgKOH / g

[0222] ZFR-1533H (manufactured by Nippon Kayaku Co., Ltd.): Bisphenol F epoxy acrylate, diethylene glycol monoethyl ether acetate solution with a solid content of 68%, anhydride modified, acid value 70 mgKOH / g, weight average molecular weight: 14000

[0223] (D) Component Photopolymerization Initiator

[0224] IC819 (manufactured by BASF Japan Ltd.): Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide

[0225] OXE-01 (manufactured by BASF Japan Ltd.): 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyl oxime)]

[0226] (E) Component: Silicon dioxide

[0227] SOC2 (manufactured by Advantex Co., Ltd.): spherical fused silica surface-treated with a phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”), average particle size 0.5 mm

[0228] SOC1 (manufactured by Advantex Co., Ltd.): spherical fused silica surface-treated with a phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”), average particle size 0.24 mm)

[0229] (F) Component Curing Accelerator

[0230] DMAP (Wako Pure Chemical Industries, Ltd.): 4-dimethylaminopyridine, MEK solution containing 2% by mass of nonvolatile components

[0231] Co(III) (Tokyo Chemical Industry Co., Ltd.): Cobalt(III) acetylacetonate, MEK solution containing 1% by mass of nonvolatile components

[0232] 2P4MZ (manufactured by Shikoku Chemicals Co., Ltd.): 2-phenyl-4-methylimidazole, DMF solution containing 5% by mass of nonvolatile components

[0233] (G) Rubber particles

[0234] AC3816N (Gantsu Chemical Co., Ltd.): Core-sheath type rubber particles

[0235] (H) Component: Photosensitizer

[0236] ·DETX-S (manufactured by Nippon Kayaku Co., Ltd.): 2,4-diethylthioxanthone

[0237] (I) Component Solvent

[0238] IP150 (solvent oil)

[0239] MEK (methyl ethyl ketone).

[0240] As can be seen from the results in Table 1, in the examples using the photosensitive resin composition of the present invention, a photosensitive resin composition having photosensitivity (definition and developability) and excellent insulation reliability can be provided. Furthermore, dielectric properties and water resistance are also excellent. On the other hand, in Comparative Example 1, although it has photosensitivity (definition and developability), since component (B) is not incorporated and an anhydride-modified epoxy acrylate resin is used, the insulation, dielectric properties and water resistance are poor, and it cannot be used as a resin composition for interlayer insulation.

Claims

1. A photosensitive resin composition comprising: (A) Epoxy resin, (B) at least one curing agent selected from the group consisting of an active ester curing agent, a cyanate curing agent, and a benzoxazine curing agent, and (C) a compound having a (meth)acrylate structure, (C) The acid value of the component is 20 mgKOH / g or less, (C) The component contains a compound having an epoxy group and a (meth)acrylate structure, When the nonvolatile matter of the photosensitive resin composition is 100 mass %, content of the component (C) is 1 to 25 mass %.

2. The photosensitive resin composition according to claim 1, wherein As the (A) epoxy resin, an epoxy resin that is liquid at a temperature of 20°C and an epoxy resin that is solid at a temperature of 20°C are contained together.

3. The photosensitive resin composition according to claim 1, wherein When the nonvolatile matter of the photosensitive resin composition is 100 mass %, content of the component (A) is 3 to 50 mass %.

4. The photosensitive resin composition according to claim 1, wherein When the nonvolatile matter of the photosensitive resin composition is 100 mass %, content of the component (B) is 1 to 30 mass %.

5. The photosensitive resin composition according to claim 1, wherein (C) Component contains the polymer which has a (meth)acrylate structure and has a weight average molecular weight of 500-100000. The photosensitive resin composition according to claim 1 , further comprising (D) a photopolymerization initiator. 7 . The photosensitive resin composition according to claim 1 , further comprising (E) an inorganic filler.

8. The photosensitive resin composition according to claim 7, wherein When the nonvolatile component of the photosensitive resin composition is 100 mass %, content of the (E) inorganic filler is 10 mass % or more.

9. The photosensitive resin composition according to claim 7, wherein When the nonvolatile component of the photosensitive resin composition is 100 mass %, content of the (E) inorganic filler is 85 mass % or less. 10 . The photosensitive resin composition according to claim 7 , further comprising a silazane compound.

11. The photosensitive resin composition according to claim 1, wherein The present invention further contains (E) an inorganic filler, wherein the (E) inorganic filler is an inorganic filler surface-treated with a silazane compound.

12. The photosensitive resin composition according to claim 1, which is used for an interlayer insulating layer of a multilayer printed wiring board.

13. The photosensitive resin composition according to claim 1, wherein The dielectric loss tangent of the cured product of the photosensitive resin composition is 0.005 to 0.

05.

14. The photosensitive resin composition according to claim 1, wherein The water absorption rate of the cured product of the photosensitive resin composition is 0.01 to 3%. 15 . A support-attached photosensitive film comprising the photosensitive resin composition according to claim 1 . 16 . A multilayer printed wiring board comprising a cured product of the photosensitive resin composition according to claim 1 .

17. A semiconductor device, characterized in that Use of the multilayer printed wiring board according to claim 16.

Images