TW201516087A - Photosensitive resin composition - Google Patents

Abstract

Provided is a photosensitive resin composition which exhibits excellent insulation reliability and has physical properties suitable for a buildup layer (interlayer insulating layer) of a multilayer printed wiring board, while having photosensitivity. This photosensitive resin composition contains (A) an epoxy resin, (B) one or more curing agents that are selected from the group consisting of active ester curing agents, cyanate ester curing agents and benzoxazine curing agents, and (C) a compound having a (meth)acrylate structure.

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition. More specifically, it relates to a photosensitive resin composition suitable for use in an interlayer insulating layer of a multilayer printed wiring board.

The conventional photosensitive resin composition is mainly made up of an alkali development type, and an acrylate containing an acid anhydride group or a carboxyl group is used to make it developable. However, since the acid anhydride group or the carboxyl group is easily thermally deteriorated, the cured product using the acrylate cannot obtain sufficient physical properties, and when it has an acid anhydride group or a carboxyl group, it is limited to form an insulating layer having high insulation reliability.

Here, for example, Patent Document 1 discloses a photosensitive resin composition for MEMS which contains a specific photocationic polymerization initiator and a specific epoxy resin, and the use is limited to MEMS applications, and the insulation reliability is Insufficient, in particular, it is not sufficient performance as a build-up layer of a multilayer printed wiring board. Further, Patent Document 2 discloses a photosensitive resin composition which is used for a protective film for a printed wiring board for semiconductor packaging, in which the insulation reliability of the resin composition is insufficient, and the use is limited to a protective film, and thus Multi-layer printing In the layering of the brushed wiring board, sufficient performance is still not exhibited.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-263544

[Patent Document 2] International Publication No. 2010/026927

Therefore, an object of the present invention is to provide a photosensitive resin composition which is excellent in insulation reliability and has physical properties suitable for a buildup layer (interlayer insulating layer) of a multilayer printed wiring board.

The present inventors have found that one or more hardeners comprising: (A) an epoxy resin, (B) selected from the group consisting of an active ester hardener, a cyanate hardener, and a benzoxazine hardener are used. Further, (C) a photosensitive resin composition having a compound having a (meth) acrylate structure can solve the above problems, and the present invention has been completed.

That is, the present invention encompasses the following.

[1] A photosensitive resin composition comprising: (A) an epoxy resin, (B) selected from the group consisting of an active ester curing agent, a cyanate curing agent, and a benzoic acid One or more hardeners of the group formed by the azine hardener, and (C) a compound having a (meth) acrylate structure.

[2] The photosensitive resin composition according to the above [1], wherein the (A) epoxy resin is used in combination and contains an epoxy resin which is liquid at a temperature of 20 ° C and is solid at a temperature of 20 ° C. Epoxy resin.

[3] The photosensitive resin composition according to the above [1] or [2], wherein the content of the component (A) is 3 to 50 when the nonvolatile component of the photosensitive resin composition is 100% by mass. quality%.

[4] The photosensitive resin composition according to any one of the above [1], wherein the content of the component (B) when the nonvolatile component of the photosensitive resin composition is 100% by mass It is 1 to 30% by mass.

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

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

[7] The photosensitive resin composition according to any one of the above [1], wherein the (C) component has an acid value of 20 mgKOH/g or less.

[10] The photosensitive resin composition according to any one of the above [1], wherein the content of the component (C) when the nonvolatile component of the photosensitive resin composition is 100% by mass It is 1 to 25% by mass.

[9] The photosensitive resin composition according to any one of the above [1] to [8] further comprising (D) a photopolymerization initiator.

[10] The photosensitive resin composition according to any one of [1] to [9] above, Further, it further contains (E) an inorganic filler.

[11] The photosensitive resin composition according to the above [10], wherein the content of the (E) inorganic filler is 10 to 85% by mass when the nonvolatile content of the photosensitive resin composition is 100% by mass. .

[12] The photosensitive resin composition according to the above [10], wherein the content of the (E) inorganic filler is 50 to 85% by mass when the nonvolatile content of the photosensitive resin composition is 100% by mass. .

[13] The photosensitive resin composition according to any one of the above [1] to [12] which is used for an interlayer insulating layer of a multilayer printed wiring board.

[14] The photosensitive resin composition according to any one of [1] to [13] wherein the cured product of the photosensitive resin composition has a dielectric tangent of 0.005 to 0.05.

[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%.

[16] A photosensitive film having a support, which comprises the photosensitive resin composition according to any one of [1] to [15] above.

[17] A multilayer printed wiring board comprising the cured product of the photosensitive resin composition according to any one of the above [1] to [15].

[18] A semiconductor device characterized by using the multilayer printed wiring board of the above [17].

According to the present invention, it is possible to provide photosensitivity while also providing excellent insulation reliability, and has a layer suitable for multilayer printed wiring boards. Physical resin composition. In addition, the photosensitive resin composition of the present invention can provide a layer which is excellent in dielectric properties, suppresses power consumption, and can provide a layer which is excellent in water resistance and heat resistance.

[Best Practice for Carrying Out the Invention]

Hereinafter, the present invention will be described in detail based on suitable embodiments.

[Photosensitive Resin Composition]

The photosensitive resin composition of the present invention contains (A) an epoxy resin and (B) one selected from the group consisting of an active ester curing agent, a cyanate curing agent, and a benzoxazine curing agent. The above hardener and (C) a compound having a (meth) acrylate structure.

Hereinafter, the components (A) to (C) contained in the resin composition of the present invention will be described.

<(A) component>

The component (A) is an epoxy resin.

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, and dicyclopentadiene. Epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, phenolic novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol Type epoxy resin, bismuth type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, Epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane dimethanol epoxy resin, and naphthyl ether epoxy resin And trimethylol type epoxy resin. The epoxy resin may be used singly or in combination of two or more.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, it is preferably at least 50% by mass or more of an epoxy resin having two or more epoxy groups in one molecule.

Further, it is preferable to include an epoxy resin (hereinafter referred to as "liquid epoxy resin") which is liquid at a temperature of 20 ° C and an epoxy resin which is solid at a temperature of 20 ° C (hereinafter referred to as "solid" Epoxy resin"). As the epoxy resin, a resin composition having excellent flexibility can be obtained by using a liquid epoxy resin and a solid epoxy resin in combination. Further, the breaking strength of the insulating layer formed by hardening the resin composition is also enhanced.

The liquid epoxy resin is preferably a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, or a naphthalene type epoxy resin, and is preferably a bisphenol A type epoxy resin. Resin, bisphenol F type epoxy resin, or naphthalene type epoxy resin. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "EXA4032SS", "HP4032SS" (naphthalene epoxy resin) manufactured by DIC Co., Ltd., and Mitsubishi Chemical Co., Ltd. "jER828EL" (bisphenol A type epoxy tree) "Liquid", "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "ZX1059" made of Nippon Steel Chemical Co., Ltd. (bisphenol A type epoxy resin and double Mixture of phenolic F-type epoxy resin). As the liquid epoxy resin, "HP4032SS" (naphthalene type epoxy resin) and "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) are particularly preferable. The liquid epoxy resin may be used singly or in combination of two or more.

As the solid epoxy resin, a tetrafunctional naphthalene epoxy resin, a cresol novolac epoxy resin, a dicyclopentadiene epoxy resin, a trisphenol epoxy resin, a naphthol novolac epoxy resin, and a biphenyl are preferable. Epoxy resin, or naphthyl ether epoxy resin, preferably 4-functional naphthalene epoxy resin, biphenyl epoxy resin, or naphthyl ether epoxy resin, more preferably biphenyl type Epoxy resin. Specific examples of the solid epoxy resin include "HP-4700" manufactured by DIC Co., Ltd., "HP-4710" (4-functional naphthalene epoxy resin), and "N-690" (cresol novolac) Type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP7200", "HP7200H", "HP7200K-65I" (dicyclopentadiene type epoxy resin), "EXA7311", " "EPA-502H" (trisphenol epoxy resin) and "NC7000L" (naphthol novolac epoxy resin) manufactured by Nippon Chemical Co., Ltd., "EXA7311-G3", "HP6000" (strandyl ether epoxy resin) ), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475" (naphthol novolac type epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd., "ESN485" (naphthol phenolic epoxy resin), manufactured by Mitsubishi Chemical Corporation "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (dixylenol type epoxy resin), etc.

In particular, "YX4000HK" (dixylenol type epoxy resin), "NC3000L" (biphenyl type epoxy resin) made by Nippon Kayaku Co., Ltd., and "HP7200H" (dicyclopentadiene) made by DIC Co., Ltd. Type epoxy resin) is preferred. The solid epoxy resin may be used singly or in combination of two or more.

When the liquid epoxy resin and the solid epoxy resin are used together as the epoxy resin, the mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1: 4 range.

When the ratio of the amount of the liquid epoxy resin to the solid epoxy resin is within this range, the following effects can be obtained: i) when used in the form of a film, moderate adhesion can be obtained, ii) followed by film When it is used, it can obtain sufficient flexibility and improve workability, and iii) an insulating layer or the like having sufficient breaking strength. From the viewpoint of the effects of the above i) to iii), the ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably 1 in mass ratio. The range of 0.3~1:3.5, more preferably the range of 1:0.6~1:3, especially the range of 1:0.8~1:2.5.

When the non-volatile content in the photosensitive resin composition is 100% by mass, the content of the epoxy resin is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 45% by mass, more preferably Preferably, it is 7 mass% to 35 mass%, and particularly preferably 8 mass% to 20 mass%.

The epoxy equivalent of the epoxy resin is preferably from 50 to 3,000, and is preferably further It is 80~2000, more preferably 110~1000. When it is within this range, an insulating layer having a sufficient crosslinking density of the cured product and excellent heat resistance can be obtained. Further, the epoxy equivalent can be measured in accordance with JIS K7236, which is a mass of a resin containing 1 equivalent of an epoxy group.

<(B) component>

The component (B) is selected from the group consisting of an active ester curing agent, a cyanate curing agent, and a benzoxazine curing agent.

-Active ester hardener -

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 when the cured product is formed, and is particularly excellent in dielectric properties and water resistance. The active ester curing agent is not particularly limited, and is preferably a compound having two or more active ester groups in one molecule. As the active ester curing agent, it is preferred to use two or more ester groups having high reactivity in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds. Compound.

From the viewpoint of improving the heat resistance in the case of forming a cured product, it is preferred to use a carboxylic acid compound and/or a thiocarboxylic acid compound, a hydroxy compound and/or a thiol compound as a reactive ester hardener. The active ester compound obtained from the reactant is preferably an active ester compound obtained from a carboxylic acid compound and a hydroxy compound, more preferably an active ester compound obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound. also, Further, it is more preferably an aromatic compound having two or more active ester groups in one molecule obtained from a reaction product of a carboxylic acid compound and an aromatic compound having a phenolic hydroxyl group. Further, the active ester curing agent is more preferably an aromatic compound obtained by reacting a compound having at least two or more carboxylic acids in one molecule with an aromatic compound having a phenolic hydroxyl group, and the aromatic compound An aromatic compound having two or more active ester groups in one molecule. Further, the active ester compound may be linear or branched. Further, a compound having at least two or more carboxylic acids in one molecule can improve the compatibility with the resin composition as long as it is a compound containing an aliphatic chain, and can improve heat resistance as long as it is a compound having an aromatic ring. . The active ester curing agent may be used alone or in combination of two or more.

Examples of the carboxylic acid compound to be used include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyrogolite. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred from the viewpoint of improvement in heat resistance at the time of forming a cured product. It is isophthalic acid and terephthalic acid. Examples of the thiocarboxylic acid compound include sulfuric acid, thiobenzoic acid, and the like.

Specific examples of the phenol compound or the naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalein, methylated bisphenol A, and methylation. 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, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, 1,3,5- Phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound (polycyclopentadiene type diphenol compound), phenol novolac, and the like.

Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol are preferred from the viewpoint of improvement in heat resistance and improvement in solubility when a cured product is formed. F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxy Phenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, 1,3,5-benzenetriol, benzenetriol, dicyclopentadiene type diphenol compound (polycyclopentadiene type II) Phenolic compound), phenol phenolic; preferably catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl Ketone, tetrahydroxydiphenyl ketone, 1,3,5-benzenetriol, benzenetriol, dicyclopentadiene type diphenol compound (polycyclopentadiene type diphenol compound), phenol novolac; Preferred are 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, dicyclopentanyl a diene-type diphenol compound (a polycyclopentadiene type diphenol compound), a phenol novolac; more preferably a 1,5-dihydroxynaphthalene 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type diphenol compound (polycyclopentadiene type diphenol compound), phenol novolac; more preferably 1,5- Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type diphenol compound (polycyclopentadiene type diphenol compound); particularly preferably dicyclopentadiene type Diphenol compound (polycyclopentadiene type diphenol compound). Specific examples of the thiol compound include phenyldithiol and triazinedithiol.

As an activity comprising a dicyclopentadiene-type diphenol condensation structure More specifically, the ester hardener is a compound represented by the following formula (1).

In the formula (1), two R's are each independently a phenyl group or a naphthyl group. The k system is represented as 0 or 1. The average repeating unit of n is 0.05 to 2.5.

From the viewpoint of lowering the dielectric tangent and improving the heat resistance, R is preferably a naphthyl group. k is preferably 0. Further, n is preferably 0.25 to 1.5.

As the active ester curing agent, an active ester compound disclosed in JP-A-2004-277460 or a commercially available active ester curing agent can be used. As an example of a commercially available active ester curing agent, specifically, an active ester curing agent containing a dicyclopentadiene type diphenol condensation structure, an active ester curing agent containing a naphthalene structure, and an acetal containing phenol novolac are preferable. An active ester hardener, an active ester hardener comprising a benzophenone benzoate, and further preferably an active ester hardener comprising a naphthalene structure, a diphenol compound comprising a dicyclopentadiene type (polycyclopentadiene) An active ester hardener of the type bisphenol compound). Examples of the active ester curing agent containing a dicyclopentadiene type diphenol compound (polycyclopentadiene type diphenol compound) structure include EXB9451, EXB9460, EXB9460S, and HPC8000-65T (manufactured by DIC). Examples of the active ester curing agent containing a naphthalene structure include, for example, EXB9416-70BK (manufactured by DIC Co., Ltd.); and an active ester curing agent containing acetaldehyde of phenol novolac, which can be listed. For example, DC808 (manufactured by Mitsubishi Chemical Corporation); and an active ester curing agent of benzamidine containing phenol novolac, for example, YLH1026 (manufactured by Mitsubishi Chemical Corporation) can be mentioned. In particular, HPC8000-65T (an active ester curing agent comprising a dicyclopentadiene type diphenol compound (polycyclopentadiene type diphenol compound) structure) is preferably used.

-Cyanate hardener -

The cyanate curing agent used in the photosensitive resin composition of the present invention can improve heat resistance, dielectric properties, and water resistance when formed into a cured product, and is particularly excellent in heat resistance. The cyanate-based curing agent is not particularly limited, and examples thereof include a cGMP type (phenol novolak type, an alkylphenol novolak type, etc.) cyanate type curing agent, and a dicyclopentadiene type cyanate type curing agent. A bisphenol type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate type curing agent, and a part of a triazine-based prepolymer. The weight average molecular weight of the cyanate-based curing agent is not particularly limited, but is preferably 500 to 4,500, and more preferably 600 to 3,000. Specific examples of the cyanate-based curing agent include bisphenol A dicyanate and polyphenol cyanate (oligo(3-methylene-1,5-phenylene)). 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2, 2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl) sulfide, bis(4-cyanate phenyl) ether 2-functional cyanate resin, phenolic phenolic phenol, cresol novolac, phenolic tree containing dicyclopentadiene A polyfunctional cyanate resin derived from a fat or the like, or a cyanate resin is a prepolymer which is subjected to a part of triazineization. These may be used alone or in combination of two or more. As a commercially available cyanate resin, a part or all of a phenol novolac type polyfunctional cyanate resin (manufactured by Lonza Japan Co., Ltd., PT30S) or bisphenol A dicyanate can be triazineized into three. A prepolymer of a polymer (manufactured by Lonza Japan Co., Ltd., BA230S75), a cyanate resin containing a dicyclopentadiene structure (manufactured by Lonza Japan Co., Ltd., DT-4000, DT-7000), or the like. In particular, "PT30S" (phenol novolac type polyfunctional cyanate resin) manufactured by Lonza Japan Co., Ltd. and "BA230S75" (partial or all of bisphenol A dicyanate are triazineized to be trimer) Prepolymers are preferred.

-benzoxazine hardener -

The benzoxazine hardener used in the photosensitive resin composition of the present invention can improve the heat resistance, dielectric properties, and water resistance when the cured product is formed. The benzoxazine hardening agent is not particularly limited, and specific examples thereof include Fa-type benzoxazine, Pd-type benzoxazine (manufactured by Shikoku Chemical Co., Ltd.), and HFB2006M (Showa Polymer (share) In particular, Pd-type benzoxazine (manufactured by Shikoku Chemicals Co., Ltd.) is preferred.

The above-mentioned active ester curing agent, the above-mentioned cyanate curing agent, and the above-mentioned benzoxazine curing agent may be used singly or in combination of two or more kinds. In particular, in terms of reducing the dielectric tangent or water absorption, an active ester hardener is preferred.

The content of the component (B) is such that the photosensitive resin composition is not volatile. When the content is 100% by mass, it is preferably from 1 to 30% by mass, more preferably from 3 to 25% by mass, even more preferably from 5 to 20% by mass.

<(C) component>

The component (C) is a compound having a (meth) acrylate structure.

The compound having a (meth) acrylate structure is not limited thereto, and examples thereof include a hydroxyalkyl acrylate such as 2-hydroxyethyl acrylate or 2-hydroxybutyl acrylate, and ethylene. a single or diacrylate of a diol such as an alcohol, ethoxytetraethylene glycol, polyethylene glycol or propylene glycol, or a propylene such as N,N-dimethyl acrylamide or N-methylol acrylamide. Alkyl alkyl acrylate such as guanamine or N,N-dimethylaminoethyl acrylate, polyhydric alcohol such as trimethylolpropane, neopentyl alcohol or dipentaerythritol or the like a polyvalent acrylate such as an adduct of ethylene oxide, propylene oxide or ε-caprolactone, a phenol such as phenoxy acrylate or phenoxyethyl acrylate, or an ethylene oxide thereof An acrylate such as a propylene oxide adduct, an epoxy acrylate derived from a glycidyl ether such as trimethylolpropane triglycidyl ether, a melamine acrylate, and/or a acrylate corresponding thereto Methacrylates, etc. Among these, polyvalent acrylates or polyvalent methacrylates are preferable, and examples thereof include trivalent acrylates or methacrylates, and examples thereof include trimethylolpropane tris(A). Acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane EO addition tris(meth)acrylate, glycerin PO addition tris(meth)acrylate, pentaerythritol IV (meth) acrylate, tetradecyl oligo (meth) acrylate, ethyl carbitol oligo (A) Acrylate, 1,4-butanediol oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate, trimethylolpropane oligo(meth)acrylate, neopentyl Tetraol oligo (meth) acrylate, tetramethylol methane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, N, N, N', N'- 肆 (β- (meth)acrylate of hydroxyethyl)ethyldiamine; etc.; as a trivalent or higher acrylate or methacrylate, for example, tris(2-(methyl) propylene oxyethyl) Phosphate, tris(2-(meth)acryloxypropyl)phosphate, tris(3-(methyl)propenyloxypropyl)phosphate, tris(3-(methyl)propene oxime -2-hydroxyoxypropyl)phosphate, bis(3-(methyl)propenyl-2-hydroxyoxypropyl)(2-(methyl)propenyloxyethyl)phosphate, (3 A phosphotriester (meth) acrylate such as (meth) propylene fluoren-2-hydroxyoxypropyl) bis(2-(methyl) propylene oxyethyl) phosphate. In order to improve the crosslinkability, water resistance or heat resistance of the cured product, the component (C) preferably has an epoxy group. In particular, "the cresol structure having a cresol novolac structure and an epoxy group" synthesized in Synthesis Example 1, "having a bisphenol structure, a biscresol structure, and an epoxy group" synthesized in Synthesis Example 2 A methacrylate compound is particularly preferred. These (meth) acrylate compounds may be used alone or in combination of two or more.

The component (C) is preferably a polymer having a (meth) acrylate structure having a weight average molecular weight of 500 to 100,000, more preferably 700 to 70,000, more preferably in terms of analytical improvement. 1000~50000, especially good 1500~35000.

Further, the weight average molecular weight of the present invention is measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). The weight average molecular weight by the GPC method, specifically, the LC-9A/RID-6A manufactured by Shimadzu Corporation using a measuring device, and the Shodex K-800P/K-804L/K manufactured by Showa Denko Co., Ltd. -804L, the mobile phase is chloroform, etc., can be measured at a column temperature of 40 ° C, and is calculated using a calibration curve of standard polystyrene.

In the photosensitive resin composition of the present invention, in order to improve the insulation reliability, it is preferred to use a compound having no carboxyl group as the component (C), but the degree of insulation reliability of the photosensitive resin composition of the present invention is not inhibited. It may have a carboxyl group therein. For example, the acid value of the component (C) is preferably 20 mgKOH/g or less, more preferably 10 mgKOH/g or less, still more preferably 5 mgKOH/g or less, more preferably 3 mgKOH/g or less, and particularly preferably 1 mgKOH/g or less.

When the non-volatile content of the photosensitive resin composition is 100% by mass, the content of the component (C) is preferably from 1 to 25% by mass, and more preferably from 5 to 15% by mass.

In the photosensitive resin composition of the present invention, the following components can be further formulated.

<(D) Photopolymerization initiator>

In the photosensitive resin composition of the present invention, the resin composition is efficiently photocured by further containing (D) a photopolymerization initiator, whereby a cured product can be obtained. (D) a photopolymerization initiator, which is not particularly limited. For example, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2-(dimethylamino)-2-[(4- Methylphenyl)methyl]-[4-(4-morpholinyl)benzene]-1-butanone, 2-methyl-1-[4-(methylthio)benzene]-2-morpholinyl Propane-1-one, diphenyl ketone, methyl diphenyl ketone, o-benzidine benzoic acid, benzamidine ethyl ether, 2,2-diethoxyacetophenone, 2,4-di Ethyl thioxanthone, diphenyl-(2,4,6-trimethylbenzhydrazide)phosphine oxide, ethyl-(2,4,6-trimethylbenzhydrazide)phenylphosphinic acid Ester, 4,4'-bis(diethylamino)diphenyl ketone, 1-hydroxy-cyclohexyl-benzophenone, 2,2-diethoxy-1,2-diphenylethane-1- An alkyl benzophenone photopolymerization initiator such as a ketone or 1-[4-(2-hydroxyethoxy)-benzene]-2-hydroxy-2-methyl-1-propan-1-one, or a double a mercaptophosphine oxide photopolymerization initiator such as (2,4,6-trimethylbenzhydrazide)-phenylphosphine oxide, or 1,2-octanedione, 1-[4-(benzene An oxime ester photopolymerization initiator such as sulfur)-, 2-(O-benzhydrazide) or a sulfonium salt photopolymerization initiator. In particular, a mercaptophosphine oxide photopolymerization initiator such as bis(2,4,6-trimethylbenzhydrazide)-phenylphosphine oxide (manufactured by BASF Japan Co., Ltd., IC819), 1, 2 - an oxime-based photopolymerization initiator of octanedione, 1-[4-(phenylthio)-, 2-(O-benzhydrazide)] (BASF Japan, OXE-01) High sensitivity is preferred.

The photopolymerization initiator may be used alone or in combination of two or more.

(D) The amount of the photopolymerization initiator is a non-volatile component in the photosensitive resin composition, from the viewpoint of sufficiently curing the photosensitive resin composition and improving the insulation reliability. When it is 100% by mass, it is preferred to set the content to 0.1% by mass or more. It is more preferably 0.2% by mass or more, and more preferably 0.3% by mass or more. On the other hand, when the amount of the photopolymerization initiator is adjusted to prevent the decrease in dimensional stability due to the excessive sensitivity, when the nonvolatile component in the photosensitive resin composition is 100% by mass, it is contained. The amount is preferably 2% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.

<(E) Inorganic filler>

In the photosensitive resin composition of the present invention, the (E) inorganic filler is further contained, whereby the coefficient of thermal expansion can be lowered. Examples of the (E) inorganic filler include vermiculite, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, and boric acid. Aluminum, barium titanate, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium zirconate, calcium zirconate, etc., among which amorphous vermiculite, molten vermiculite, hollow germanium Stones such as stone, crystalline vermiculite, and synthetic vermiculite are particularly suitable. It is preferable that the vermiculite is a spherical vermiculite. These may be used alone or in combination of two or more. For example, "SOC2" and "SOC1" manufactured by Admatechs Co., Ltd. are preferable as the commercially available spherical molten vermiculite.

(E) The average particle diameter of the inorganic filler is preferably 1 μm or less, more preferably 0.8 μm or less, and more preferably 0.6 μm or less, in terms of improvement in insulation reliability and improvement in photocurability. Below μm is more preferred. On the other hand, in terms of preventing the aggregation of the inorganic filler, the average particle diameter of the (E) inorganic filler is 0.01 μm or more. Preferably, 0.05 μm or more is further preferred. In addition, as an inorganic filler, a decane coupling agent (epoxy decane coupling agent, an amino decane coupling agent, a mercapto decane coupling agent, etc.) and a titanate coupling agent are used in order to improve moisture resistance and dispersibility. It is preferred that the surface treatment agent such as a guanidinium compound is surface-treated. These may be used alone or in combination of two or more.

Examples of the epoxy decane coupling agent include glycidoxypropyl trimethoxy decane, glycidoxy propyl triethoxy decane, glycidoxy propyl methyl diethoxy decane, and shrinkage. Glyceryl butyl trimethoxy decane, (3, 4-epoxycyclohexyl) ethyl trimethoxy decane, etc.; as the amino decane coupling agent, for example, aminopropyl methoxy decane, amine propyl Triethoxy decane, N-phenyl-3-aminopropyltrimethoxydecane, N-2 (aminoethyl)aminopropyltrimethoxydecane, etc.; as a mercapto decane coupling agent, For example, mercaptopropyltrimethoxydecane, mercaptopropyltriethoxydecane, and the like are listed. These may be used alone or in combination of two or more. As a commercially available coupling agent, "KBM403" (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" manufactured by Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd. (N-phenyl-3-) Aminopropyltrimethoxydecane) and the like.

Examples of the titanate coupling agent include butyl titanate dimer, octanediol titanium, diisopropoxy titanium bis(triethanolamine), dihydroxy titanium dilactate, and dihydroxy bis (ammonium). Lactic acid ester) titanium, bis (dioctyl pyrophosphate) Ester) ethylene glycolitate, bis(dioctyl pyrophosphate)oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-titanate butyl ester, tetra (2) -ethylhexyl) titanate, tetraisopropylbis(dioctylphosphite) titanate, tetraoctylbis(ditridecylphosphite) titanate, tetra (2,2 -diallyloxymethyl-1-butyl)bis(bis(tridecyl)phosphite) titanate, isopropyltrioctylphosphonate, isopropyltricumylbenzene titanate , isopropyl triisostearyl decyl titanate, isopropyl isostearyl decyl bis decyl decyl titanate, isopropyl dimethyl propylene decyl isostearyl decyl titanate, isopropyl Tris(dioctyl phosphate) titanate, isopropyl tris(dodecylphenylsulfonyl) titanate, isopropyl hydrazide (dioctyl pyrophosphate) titanate, isopropyl Tris(N-Aminoethyl ‧ aminoethyl) titanate and the like. These may be used alone or in combination of two or more.

Examples of the decane alkane compound include hexamethyldiazepine, 1,3-divinyl-1,1,3,3-tetramethyldiazepine, and octamethyltriazane. Hexa(t-butyl)dioxane, hexabutyldiazepine, hexaoctyldioxane, 1,3-diethyltetramethyldiazepine, 1,3-di-n -octyltetramethyldiazepine, 1,3-diphenyltetramethyldiazane, 1,3-dimethyltetraphthalene, 1,3-diethyltetramethyl Indole, 1,1,3,3-tetraphenyl-1,3-dimethyldiazepine, 1,3-dipropyltetramethyldiazepine, hexamethylcyclotriazide Alkane, hexaphenyldioxane, dimethylaminotrimethylsulfazane, triazane, cyclotriazane, 1,1,3,3,5,5-hexamethylcyclotriene Preferably, decazane or the like is particularly preferably hexamethyldioxane. These may be used alone or in combination of two or more.

(E) Inorganic filler, the composition of the photosensitive resin composition From the viewpoint of the improvement of the bulkiness, an inorganic filler which is surface-treated with a decazane compound is preferred. Further, after surface treatment with a decazane compound, surface treatment with a decane coupling agent can further improve dispersibility. The amount of the sulfonium compound to be used for the surface treatment is preferably 0.001% by mass to 0.3% by mass, and preferably 0.005% by mass to 0.2% by mass based on 100% by mass of the inorganic filler. As the spherical molten vermiculite which is surface-treated with hexamethyldioxane, for example, "SC2050" manufactured by Admatechs Co., Ltd. is mentioned. Further, the amount of the decane coupling agent used for the surface treatment is preferably 0.1% by mass to 6% by mass based on 100% by mass of the inorganic filler, and preferably 0.2% by mass to 4% by mass, more preferably 0.3% by mass. %~3 mass% is more preferable.

(E) The average particle size of the inorganic filler can be measured by a laser diffraction ‧ scattering method according to the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis via a laser diffraction type particle size distribution measuring device, and can be measured by setting the flat median diameter to an average particle diameter. The measurement sample is preferably one in which an inorganic filler is dispersed in water via ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring device, LA-500, LA-750, or the like manufactured by Horiba, Ltd. can be used.

When the content of the (E) inorganic filler is adjusted, the non-volatile content in the photosensitive resin composition is set to 100% by mass, from the viewpoint of reducing the linear thermal expansion coefficient of the cured product and preventing the deformation of the cured product. In the case of 10% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, and more preferably 40% by mass or more, so that heat resistance is obtained. In terms of improvement, 50% by mass or more is particularly good. On the other hand, when the content of the inorganic filler is adjusted (E), the non-volatile component in the photosensitive resin composition is set to 100 in terms of prevention of reduction in alkali developability and improvement in photocurability. When the mass is %, it is preferably 85 mass% or less, more preferably 75 mass% or less, and still more preferably 65 mass% or less.

<(F) hardening accelerator>

In the photosensitive resin composition of the present invention, by further containing (F) a curing accelerator, heat resistance, adhesion, chemical resistance, and the like of the cured product can be improved.

The (F) curing accelerator is not particularly limited, and examples thereof include an amine-based curing accelerator, an oxime-based curing accelerator, an imidazole-based curing accelerator, an lanthanum-based curing accelerator, and a metal-based curing accelerator. These may be used alone or in combination of two or more.

The amine-based curing accelerator is not particularly limited, and examples thereof include a trialkylamine such as triethylamine or tributylamine, 4-dimethylaminopyridine, and benzyldimethylamine. An amine compound such as 4,6,-paraxyl (dimethylaminomethyl)phenol or 1,8-diazabicyclo (5.4.0)-undecene. These may be used alone or in combination of two or more.

The oxime-based hardening accelerator is not particularly limited, and examples thereof include dicyandiamide, 1-methyl hydrazine, 1-ethyl hydrazine, 1-cyclohexyl hydrazine, 1-phenylhydrazine, and 1-(o-toluene).胍, dimethyl hydrazine, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazabicyclo[4.4.0] 癸-5-ene, 7 -Methyl-1,5,7-triazabicyclo[4.4.0]non-5-ene, 1-methyl double Anthracene, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allyl biguanide, 1-phenylbiguanide, 1-(o-methylphenyl)biguanide, and the like. These may be used alone or in combination of two or more.

The imidazole-based hardening accelerator is not particularly limited, and examples thereof include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 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-undecylimidazolium trimellitate, 1-cyanoethyl-2-benzimidazole trimellitate, 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-phenylimidazolium isocyanide Urea acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole [1 , 2-a] benzimidazole, 1-dodecyl An imidazole compound such as 2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline or 2-benzimidazoline, and an adduct of an imidazole compound and an epoxy resin. These may be used alone or in combination of two or more.

The oxime-based hardening accelerator is not particularly limited, and examples thereof include triphenylphosphine, bismuth borate compound, and tetraphenylphosphonium tetraphenylborate. Ester, n-butyl phthalocyanate, tetrabutyl phthalate, (4-methylphenyl) triphenyl sulfonate, tetraphenyl thiocyanate, butyl triphenyl hydrazine Thiocyanate, etc. These may be used alone or in combination of two or more.

In the photosensitive resin composition of the present invention, as the curing accelerator (other than the metal-based curing accelerator), an amine-based curing accelerator or an imidazole-based curing accelerator is preferably used, and among them, 4-dimethyl methacrylate is used. The amino-aminopyridine and 2-phenyl-4-methylimidazole are particularly preferred. When the content of the non-volatile component in the photosensitive resin composition is 100% by mass, the content of the curing accelerator (excluding the metal-based hardening accelerator) is preferably in the range of 0.005 mass% to 1 mass%, and 0.01 mass%. The range of %~0.08 mass% is more preferable. When it is less than 0.005 mass%, the curing tends to be slow, and a long hardening time tends to be required. When the amount is more than 1% by mass, the storage stability of the resin composition tends to be lowered.

The metal-based hardening accelerator is not particularly limited, and examples thereof include an organometallic complex or a metal salt of a metal such as cobalt, copper, zinc, iron, nickel, manganese or tin. Specific examples of the organic metal complex compound include organic cobalt complexes such as cobalt (II) acetamidine acetone, cobalt (III) acetamidine acetone, and organic copper complexes such as copper (II) acetamidine acetone. , an organic zinc complex such as zinc (II) acetamidineacetone, an organic iron complex such as iron (III) acetamidineacetone, an organic nickel complex such as nickel (II) acetamidine acetone, or manganese (II) An organic manganese complex such as acetamidine or the like. Examples of the organic metal salt include zinc octoate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used alone or in combination of two or more.

In the photosensitive resin composition of the present invention, as the metal-based curing accelerator, an organic cobalt complex is preferably used, and in particular, cobalt (III)acetonitrile is preferably used. When the total amount of the solid content of the photosensitive resin composition is 100% by mass, the metal content of the metal-based curing catalyst is preferably in the range of 25 ppm to 500 ppm, and is preferably 30 ppm. A range of 200 ppm is also preferred.

<(G) organic filler>

In the photosensitive resin composition of the present invention, by further containing the (G) organic filler, the stress of the cured product can be alleviated, and the occurrence of chipping during the formation of the cured product can be prevented. Examples of the (G) organic filler include rubber particles, polyamide fine particles, and polyfluorene oxide particles. In the present invention, rubber particles are preferably used.

The rubber particles may be any fine particles of a resin which is subjected to a chemical crosslinking treatment to a resin exhibiting rubber elasticity and which is insoluble and insoluble in an organic solvent, and examples thereof include acrylonitrile. Ethylene rubber particles, butadiene rubber particles, acrylic rubber particles, and the like. Specific examples of the rubber particles include XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), STAPHYLOID AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, and IM101 (above, manufactured by Ganz Chemical Co., Ltd.) Paraloid. EXL 2655 and EXL 2602 (above, manufactured by Kureha Chemical Industries Co., Ltd.) and the like are preferably AC3816N (manufactured by Ganz Chemical Co., Ltd.).

The polyamide fine particles may be any fine particles of 50 μm or less, which may be a resin having a guanamine bond, and may be any of the polyamide fine particles, and examples thereof include aromatic polyamines such as nylon and aromatics such as aramid. Polyamide, polyamidoximine, and the like. Specific examples of the polyamide fine particles include VESTOSINT 2070 (manufactured by Daicel Hyuru Co., Ltd.) or SP500 (manufactured by Toray Co., Ltd.).

(G) The average particle diameter 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 using a dynamic light scattering method. (G) The average particle size of the organic filler is, for example, the organic filler is uniformly dispersed in an appropriate organic solvent via ultrasonic waves or the like, and a thick particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.) is used. The particle size distribution of the organic filler is prepared on a mass basis and can be measured by using its flat median diameter as the average particle diameter.

When the content of the organic filler in the (G) organic filler is adjusted, the solid content of the photosensitive resin composition is 100% by mass, and 0.1 is used for the improvement of the heat resistance and the improvement of the laser processing property. The mass % to 6 mass% is preferable, and the 0.5 mass% to 4 mass% is more preferable.

<(H) Photosensitizer>

As the photosensitive resin composition of the present invention, as the (H) photosensitizer, ethyl N,N-dimethylaminobenzoate and isoamyl N,N-dimethylaminobenzoate may be added. a tertiary amine such as pentyl-4-dimethylaminobenzoate, triethylamine or triethanolamine, or a pyrazoline or an anthracene Light sensitizers such as coumarins, xanthones, and thioxanthones. In the present invention, as the photosensitizer, thioxanthone is preferably used, and 2,4-diethylthioxanthone is more preferably used. The photosensitizer can be used alone or in combination of two or more.

<(I) Organic Solvent>

The photosensitive resin composition of the present invention can adjust the varnish viscosity by further containing (I) an organic solvent. Examples of the (I) organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbon groups such as toluene, xylene, and tetramethylphenyl, and methyl sulfonium and butyl groups. Glycol ethers such as cyproterone, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Ethyl acetate, butyl acetate, butyl cyproterone acetate, carbitol acetate esters, aliphatic hydrocarbon bases such as octane and decane, petroleum ether, petroleum brain, water-added petroleum brain, mineral spirits The petroleum solvent or the like is preferable, but among them, solvent oil and methyl ethyl ketone are preferred. These may be used alone or in combination of two or more. The content in the case of using an organic solvent can be appropriately adjusted from the viewpoint of coatability of the photosensitive resin composition.

<(J) Other additives>

As the other additive of (J), for example, a microparticle such as melamine or organic bentonite, a coloring agent such as indigo blue, indocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black or naphthalene black may be added. Hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc. Polymerization inhibitor, bentonite, Montestone and other tackifiers, polyfluorene-based, fluorine-based, vinyl-based defoamers, brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds Various additives such as a phosphorus-based compound, an aromatic condensed phosphate, a flame retardant such as a halogen-containing condensed phosphate, and a thermosetting resin such as a phenol-based curing agent.

The photosensitive resin composition of the present invention is suitably mixed with the above (A) to (C) (and optionally mixed (D) to (J)), and further, by a triaxial roll, a ball mill, or a bead mill as required A kneading method such as a sand mixer or a stirring method such as a super mixer or a planetary mixer can be produced by kneading or stirring to produce a resin varnish.

The use of the photosensitive resin composition of the present invention is not particularly limited, and can be used for a photosensitive film, a photosensitive film with a support, an insulating resin sheet such as a prepreg, and a circuit board (laminate use, multilayer) Printed wiring board applications, etc., solder resists, underfill materials, grain bonding materials, semiconductor sealing materials, hole-filling resins, and component encapsulating resins are widely used in applications requiring resin compositions. In particular, it can be suitably used as a resin composition for an insulating layer of a multilayer printed wiring board (a multilayer printed wiring board in which a cured product of a photosensitive resin composition is an insulating layer), and is particularly suitably used as a resin for an interlayer insulating layer. (a multilayer printed wiring board in which a cured product of a photosensitive resin composition is an interlayer insulating layer), and a resin composition for plating (a multilayer printed wiring board in which a plating is formed on a cured product of a photosensitive resin composition) .

<Photosensitive film>

The photosensitive resin composition of the present invention is applied onto a support substrate in a resin varnish state, and dried to form a resin composition layer to form a photosensitive film. Further, the photosensitive film previously formed on the support may be laminated on the support substrate and used. The photosensitive film of the present invention can be laminated on various support substrates. Examples of the support substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate.

<Photosensitive film with support>

The photosensitive resin composition of the present invention can be suitably used in the form of a photosensitive film with a support formed on a support as a layer of a resin composition layer. That is, the photosensitive film with the support is formed of a layer of a photosensitive resin composition on the support. Examples of the support include a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a polyvinyl alcohol film, and a triacetic acid acetate film. A polyethylene terephthalate film is preferred.

As a commercially available support, for example, the product name "Alphand MA-410" manufactured by Oji Paper Co., Ltd., "E-200C", Shin-Etsu Film Co., Ltd., and the like, and the Teijin Co., Ltd. The polyethylene terephthalate film such as the PS series, such as the product name "PS-25", is not limited thereto. In order to facilitate the removal of the resin composition layer, it is preferred to apply a release agent such as a polyoxyxene coating agent to the surface. The thickness of the support is preferably in the range of 5 μm to 50 μm, and more preferably in the range of 10 μm to 25 μm. If the thickness is less than 5μm, it is obvious When the support is peeled off before the shadow, the support (support film) tends to be easily broken. On the other hand, when the thickness exceeds 50 μm, the resolution at the time of exposure on the support tends to be lowered. Further, a support having a low fisheye is preferred. Here, the term "fisheye" means that when a film is produced by thermal melting, kneading, extrusion, biaxial stretching, casting, or the like, foreign matter, undissolved matter, oxidative degradation or the like of the material is mixed into the film. Into.

Further, in order to reduce light scattering during exposure by an active energy ray such as ultraviolet rays, the support is preferably excellent in transparency. Specifically, the turbidity (haze of a standardized by JIS-K6714) which is an index of transparency is preferably 0.1 to 5. Further, the resin composition layer can also be protected with a protective film.

By protecting the resin composition layer side of the photosensitive film with the support by the protective film, adhesion or scratching of foreign matter or the like on the surface of the resin composition layer can be prevented. As the 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, and is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and even more preferably in the range of 10 μm to 30 μm. When the thickness is less than 1 μm, the handleability of the protective film tends to be lowered, and if it exceeds 40 μm, the inexpensiveness tends to be poor. Further, the adhesion of the protective film to the resin composition layer and the support is preferably such that the adhesion between the resin composition layer and the protective film is small.

The photosensitive film with a support of the present invention can be prepared by a person skilled in the art according to a known method, for example, a resin in which an organic resin is dissolved in the photosensitive resin composition of the present invention. The varnish is applied to the support, and the resin varnish is dried by heating or blowing hot air to form a resin composition layer. Specifically, first, the bubbles in the photosensitive resin composition are completely removed by a vacuum defoaming method or the like, and then the photosensitive resin composition is applied onto the support, and the solvent is removed and dried by a hot air oven or a far infrared furnace. Then, a photosensitive film with a support can be produced by laminating a protective film on the obtained resin composition layer as needed. The specific drying conditions vary depending on the curability of the resin composition or the amount of the organic solvent in the resin varnish, but the resin varnish containing 30% by mass to 60% by mass of the organic solvent may be in the range of 80 ° C to 120 ° C. Dry it in 3 minutes to 13 minutes. The amount of the residual organic solvent in the resin composition layer is preferably 5% by mass or less based on the total amount of the resin composition layer in order to prevent the diffusion of the organic solvent in the subsequent step. The mass % or less is also preferred. Those skilled in the art can set appropriate and suitable drying conditions by simple experimentation. The thickness of the resin composition layer is preferably in the range of 5 μm to 500 μm, and is preferably 10 μm to 200 μm from the viewpoint of improving workability and preventing deterioration of sensitivity and resolution in the resin composition layer. The range is preferably further, and is preferably in the range of 15 μm to 150 μm, more preferably in the range of 20 μm to 100 μm, and particularly preferably in the range of 20 μm to 60 μm.

Examples of the coating method of 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, and a slit. Coating method, lip coating method, comma Coating method, doctor blade coating method, roll coating method, blade coating method, curtain coating method, chamber gravure coating method, slit coating method, spray coating method, dip coating method, and the like.

The photosensitive resin composition may be applied in several times or in one application, or may be applied in a plurality of different combinations. Among them, a die coating method which is excellent in uniform coating property is preferable. Moreover, in order to avoid the incorporation of foreign matter or the like, it is preferable to carry out the coating step in an environment where the amount of foreign matter such as a clean room is small.

<Multilayer printed wiring board>

Next, an example in which a multilayer printed wiring board is produced using a photosensitive resin composition is described.

When the interlayer insulating layer is produced by using the photosensitive resin composition of the present invention, (1) the via opening can be performed at one time, and (2) the positional accuracy of the via hole is superior to that of the laser opening.

(coating and drying steps)

The photosensitive resin composition is directly applied onto a circuit board in a resin varnish state, and a photosensitive film is formed on a circuit board by drying the organic solvent. Examples of the circuit board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Here, the circuit board refers to a substrate in which a patterned conductor layer (circuit) is formed on one surface or both surfaces of the substrate as described above.

Further, in the multilayer printed wiring board formed by alternately laminating the conductor layer and the insulating layer, one or both of the outermost layers of the multilayer printed wiring board are substrates of the conductor layer (circuit) processed by the pattern, and are also included in In the so-called circuit substrate. Further, the surface of the conductor layer may be subjected to a roughening treatment in advance by blackening treatment, copper etching, or the like.

As the coating method, generally, the full printing by the screen printing method is often used, but any other method may be used as long as it is a coating method which can be uniformly applied. For example: spray coating method, hot melt coating method, rod coating method, applicator method, blade coating method, blade coating method, air knife coating method, curtain coating method, roll coating method, gravure The coating method, the lithography method, the dip coating method, the brush coating, and other general coating methods can all be used. After coating, it is dried in a hot air oven or a far infrared furnace as needed. The drying conditions are preferably set at 80 ° C to 120 ° C for 3 minutes to 13 minutes. A photosensitive film can be formed on the circuit substrate in such a manner.

(Lamination step)

Further, when a photosensitive film having a support is used, the resin composition layer side is laminated on one surface or both surfaces of the circuit board using a vacuum laminator. In the laminating step, when the photosensitive film with the support is provided with a protective film, after the protective film is removed, the resin composition layer is pressurized and heated in response to the required preheating of the photosensitive film and the circuit substrate. At the same time, the pressure is adhered to the circuit substrate. For the photosensitive film of the present invention, a method of laminating on a circuit board under a reduced pressure environment by vacuum lamination is suitable use.

The conditions of the laminating step are not particularly limited. For example, the pressure-bonding temperature (laminating temperature) is preferably set to 70 ° C to 140 ° C, and the pressure-adhesive pressure is preferably 1 kgf / cm ² to 11 kgf / cm ² ( 9.8×10 ⁴ N/m ² ~107.9×10 ⁴ N/m ² ), the pressure-bonding time is preferably set in a reduced pressure environment with a setting of 5 seconds to 300 seconds and an air pressure of 20 mmHg (26.7 hPa) or less. It is better. Further, the laminating step may be a batch type or a continuous type using a roll. Vacuum lamination can be carried out using a commercially available vacuum laminator. Examples of the commercially available vacuum laminating machine include a vacuum laminator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Nippon Seiki Co., Ltd., and a dry coating of a roll made by Hitachi Industries. Cloth, Hitachi AIC (share) vacuum laminating machine, etc. In this manner, a photosensitive film can be formed on the circuit board.

(exposure step)

After the photosensitive film is provided on the circuit board by the coating and drying step or the laminating step, the specific portion of the resin composition layer is irradiated with the active light ray by the mask pattern, and the resin composition of the illuminating portion is performed. The layer is exposed to light hardening. Examples of the active light include ultraviolet rays, visible light, electron rays, and X-rays, and ultraviolet rays are particularly preferable. The amount of ultraviolet rays irradiated is approximately 10 mJ/cm ² to 1000 mJ/cm ² . The exposure method includes a contact exposure method in which a mask pattern is adhered to a printed wiring board, and a non-contact exposure method in which parallel light is used for exposure without being in close contact, but it may be used. Further, when a support is present on the resin composition layer, exposure may be performed on the support, or the support may be peeled off and then exposed.

(development step)

After the exposure step, when the support is present on the resin composition layer, the support is removed, and the uncured portion (unexposed portion) is removed by wet development or dry development, and development is carried out to form a pattern. type.

In the case of the above-mentioned wet development, a developer which is safe, stable, and workable, such as an alkaline aqueous solution, an aqueous developing solution, or an organic solvent, can be used as the developing solution, and in the present invention, it is carried out by an organic solvent. The development step is preferred. Further, as the developing method, a well-known method such as spraying, shaking immersion, brushing, and blade coating can be suitably employed.

An organic solvent as a developing solution can be used, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether.

The concentration of the organic solvent is preferably 2% by mass to 90% by mass based on the total amount of the developer. Moreover, the temperature of such an organic solvent can be adjusted in accordance with developability. Further, such an organic solvent may be used singly or in combination of two or more types. Examples of the organic solvent-based developing solution used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylamine, cyclohexanone, and methyl isobutylene. Peptone, γ-butyrolactone, propylene glycol 1-monomethyl ether 2-acetate (PGMEA), PGMEA is preferred in the present invention.

In the formation of the pattern of the present invention, the above-described two or more types of development methods may be used in combination. For the development method, there are a dipping method, a stirring method, a spraying method, a high-pressure spraying method, a brushing method, a slap, etc., and it is suitable for a high-pressure spraying method for improving the resolution. The spray pressure at the time of spraying is preferably 0.05 MPa to 0.3 MPa.

(post-baking step)

After the above development step is completed, a post-baking step is performed and an insulating layer (cured material) is formed. Examples of the post-baking step include an ultraviolet irradiation step through a high-pressure mercury lamp or a heating step using a clean oven. When the ultraviolet ray is irradiated, the irradiation amount can be adjusted as needed, and for example, irradiation can be performed at an irradiation amount of about 0.05 J/cm ² to 10 J/cm ² . Further, the heating condition may be appropriately selected in accordance with the type and content of the resin component in the resin composition, and may preferably be in the range of from 20 minutes to 180 minutes at 150 ° C to 220 ° C. Jia is in the range of 30 minutes to 120 minutes at 160 ° C ~ 200 ° C.

(plating step)

Next, a conductor layer can be formed on the insulating layer by dry plating or wet plating. As the dry plating, a well-known method such as a vapor deposition method, a sputtering method, or an ion deposition method can be used. In the vapor deposition method (vacuum vapor deposition method), for example, a support is placed in a vacuum vessel, and a metal film can be formed on the insulating layer by heating and evaporating the metal. The sputtering method is also, for example, a support body is placed in a vacuum vessel, an inert gas such as argon is introduced, and a direct current voltage is applied to make it separate. The inert gas collides with the target metal, and a metal film can be formed on the insulating layer by the flying metal.

In the case of wet plating, the surface of the formed insulating layer is formed by the swelling treatment of the swelling liquid, the roughening treatment of the oxidizing agent, and the neutralization treatment of the neutralizing liquid to form an uneven anchor (anchor) ). The swelling treatment of the swelling liquid is carried out by immersing the insulating layer in the swelling liquid at 50 ° C to 80 ° C for 5 minutes to 20 minutes. The swelling solution may, for example, be an alkali solution, and examples of the alkali solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of the commercially available swelling liquid include, for example, Atotech Japan, Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, and the like. The oxidizing agent is immersed in an oxidizing agent solution at 60 ° C to 80 ° C for 10 minutes to 30 minutes by roughening the oxidizing agent. The oxidizing agent may, for example, be an alkaline permanganic acid solution, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid or the like in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. Further, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by weight to 10% by weight. The commercially available oxidizing agent may, for example, be an alkaline permanganic acid solution such as concentrates Compact CP manufactured by Atotech Japan Co., Ltd. or Dosing Solution security Gans P. The neutralization solution is neutralized at 30 ° C to 50 ° C for 3 minutes to 10 minutes to be immersed in the neutralizing solution. As a neutralizing liquid, an acidic aqueous solution is preferable, and as a commercial item, a reduction solution Shin security by Atotech Japan Co., Ltd. is mentioned. Gantt P.

Next, electroless plating and electrolytic plating are combined to form a conductor layer. Further, a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As a method of forming the pattern later, for example, an erasing method, a semi-additive method, and the like which are well known to those skilled in the art can be used.

<semiconductor device>

A semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention. In the conduction portion of the multilayer printed wiring board of the present invention, a semiconductor device can be manufactured by mounting a semiconductor wafer. The term "conducting portion" means "a portion of an electrical signal in a conductive printed wiring board", and the position thereof may be any surface or a portion to be filled. Further, the semiconductor wafer is not particularly limited as long as it is a circuit element made of a semiconductor.

The method of mounting the semiconductor wafer in the case of manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor wafer can function effectively, and specific examples thereof include a wire bonding mounting method, a flip chip mounting method, and a flip chip mounting method. The method of mounting without bumps (BBUL), the method of mounting an anisotropic conductive film (ACF), the method of mounting by a non-conductive film (NCF), and the like.

The photosensitive resin composition of the present invention can provide a resin composition which is excellent in insulation reliability and has physical properties suitable for layering of a multilayer printed wiring board. Furthermore, it is excellent in dielectric properties, water resistance and heat resistance, and is suitable for development in an organic solvent. Compound. The characteristics of these are detailed below.

The dielectric tangent of the cured product of the photosensitive resin composition of the present invention can be measured by <measurement of dielectric properties> to be described later. Specifically, dielectric tangential measurement can be performed by a cavity resonance perturbation method in which the number of cycles is 5.8 GHz and the measurement temperature is 23 °C. From the viewpoint of preventing high-frequency heating, reducing signal delay, and signal noise, the dielectric tangent is preferably 0.05 or less, 0.04 or less is preferable, 0.03 or less is more preferable, and 0.02 or less is more preferable. Below 0.013 is especially better. On the other hand, the lower limit of the dielectric tangent is not particularly limited to 0.005 or more.

The water resistance (water absorption rate) of the cured product of the photosensitive resin composition of the present invention can be measured by a measurement method described in <Measurement of Water Resistance> to be described later. The water absorption rate is preferably 3% or less, more preferably 2% or less, and more preferably 1% or less, from the viewpoint of prevention of generation of voids in the production of a printed wiring board and improvement in insulation reliability. % below is even better. On the other hand, the lower limit of the water absorption rate is not particularly limited, and is 0.01% or more, 0.1% or more, 0.2% or more, and the like.

The heat resistance of the cured product of the photosensitive resin composition of the present invention can be measured by a measurement method described in <Evaluation of Heat Resistance> to be described later. As an index of heat resistance, it is preferable to use a glass transition point from the viewpoint of preventing deterioration of a cured product when a cured product is subjected to a heat history. The glass transition point is preferably 110 ° C or higher. The upper limit of the glass transition point is not particularly limited, and is preferably 300 ° C or less. Moreover, as a point of prevention of deformation of the printed wiring board, it is also an indicator of heat resistance. Use the coefficient of thermal expansion. The coefficient of thermal expansion is preferably 10 to 30 ppm/°C.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples. Still, "parts" means the quality.

<Adjustment of laminate for evaluation>

The copper layer of the glass epoxy substrate of the circuit formed of the copper layer having a thickness of 18 mm was subjected to roughening treatment by CZ8100 (surface treatment agent containing organic acid, manufactured by Mec). Then, the resin composition layer of the photosensitive film with the support obtained in the examples and the comparative examples was brought into contact with the surface of the copper circuit, and a vacuum laminator (manufactured by Nichigo-Morton Co., Ltd., VP160) was used. The laminate is formed by laminating the glass epoxy substrate, the resin composition layer, and the laminate in the order of the support. The pressure-bonding condition was carried out after evacuation for 20 seconds, at a pressure-bonding temperature of 80 ° C, a pressure-pressure of 0.2 MPa, and a press time of 20 seconds. The laminate was allowed to stand at room temperature for 1 hour or more. From the support of the laminate, a circular hole pattern was used and a circular hole having a diameter of 80 mm was formed, and a pattern forming device was used to irradiate ultraviolet rays of 100 mJ/cm ² . Exposure. After standing at room temperature for 30 minutes, the support was peeled off from the laminate. In the embodiment, the resin composition layer on the laminate is completely immersed in PGMEA (propylene glycol 1-monomethyl ether 2-acetate) as a developing solution at 30 ° C and developed, and then the developer is wiped off. Ultraviolet irradiation of 1 J/cm ² was performed, and heat treatment was performed at 190 ° C for 60 minutes, and an insulating layer having an opening of 80 mm in diameter was formed on the laminate. This was used as a laminate for evaluation.

On the other hand, in the comparative example, for the entire resin composition layer on the laminate, a 1% by mass sodium carbonate aqueous solution of 30 ° C as a developing solution was sprayed at a pressure of 0.15 MPa and a minimum development time (unexposed portion was developed). Spray development was performed 1.5 times the minimum time). After the spray development, ultraviolet irradiation was performed at 1 J/cm ² , and heat treatment was performed at 190 ° C for 60 minutes, and an insulating layer having an opening of 80 mm in diameter was formed on the laminate.

<Adjustment of hardened material for evaluation>

The resin composition layer of the photosensitive film with a support obtained in the examples and the comparative examples was subjected to photocuring by exposure to ultraviolet rays of 100 mJ/cm ² . Thereafter, the resin composition layer was subjected to ultraviolet irradiation of 1 J/cm ² in total, and further heat treatment was performed at 190 ° C for 90 minutes to form an insulating layer. Thereafter, the support was peeled off as a cured product for evaluation.

<Measurement method ‧ Evaluation method>

First, various measurement methods and evaluation methods will be described.

<Evaluation of photosensitivity> (analytical)

In the analytic evaluation, the photoresist shape of the round hole of the evaluation laminate was observed by SEM (magnification: 1000 times), and the following criteria were used. Evaluation.

○: The shape of the round hole was good, and it was not rolled up or peeled off.

×: The shape of the circular hole is enlarged by development, and it is rolled up or peeled off.

(developability)

In the evaluation of the developability, the residue at the bottom of the round hole of the laminate for evaluation was observed by SEM (magnification: 1000 times), and the presence or absence of the residue at the bottom of the round hole was evaluated by the following criteria.

○: There was no development residue on the substrate having a circular hole diameter of 80 mm, and the development residue removal property was excellent.

X: There was a development residue on a substrate having a circular hole having a diameter of 80 mm, and the development residue removal property was poor.

<Evaluation of insulation reliability>

On the yttrium imide film formed with the comb-shaped electrode (line width/pitch=15 μm/15 μm), the resin composition layer of the photosensitive film with the support obtained in the examples and the comparative examples and the copper circuit were used. The surface was joined to each other by a vacuum laminator (manufactured by Nichigo-Morton Co., Ltd., VP160). The pressure-bonding condition was carried out after evacuation for 20 seconds, at a pressure-bonding temperature of 80 ° C, a pressure-pressure of 0.2 MPa, and a press time of 20 seconds. The laminate was allowed to stand at room temperature for 1 hour or more, and the support of the laminate was exposed to ultraviolet rays of 100 mJ/cm ² . After standing at room temperature for 30 minutes, the support was peeled off from the laminate. Thereafter, ultraviolet irradiation was performed at 1 J/cm ² , and heat treatment was performed at 190 ° C for 60 minutes to obtain a laminate for evaluation. This evaluation laminate was placed in a high-temperature and high-humidity bath under a gas atmosphere of 130 ° C and a humidity of 85%, and the charging voltage was 3.3 V, and the HAST test was carried out in the tank over 100 hours. The insulation resistance value of the laminate for evaluation after 100 hours passed was evaluated based on the following criteria.

○: 10 ⁸ Ω or more

×: 10 ⁸ Ω or less

<Measurement of dielectric properties> (dielectric tangent)

The cured product for evaluation was cut into a length of 80 mm and a width of 2 mm to obtain Evaluation Sample 1. With respect to this evaluation sample 1, the dielectric tangent was measured by a cavity resonance perturbation method using a measurement of the cycle number of 5.8 GHz and a measurement temperature of 23 ° C using a HP8362B apparatus manufactured by AGILENT TECHNOLOGIES. The measurement was performed on two evaluation samples 1 and the average value was calculated.

<Measurement of water resistance> (water absorption rate)

The cured product for evaluation was cut into 5 cm squares as Evaluation Sample 2. Next, the mass of the evaluation sample 2 was measured, and the evaluation sample after the mass measurement was placed in pure water in a boiling state, and left to stand for 1 hour in a state in which the evaluation sample 2 was completely immersed. Thereafter, the evaluation sample 2 was taken out, and the moisture on the surface was sufficiently wiped off, and the mass after the water absorption was measured to 0.1 mg, and the water resistance WA (%) was determined by the following formula. For 4 evaluation samples 2 to measure and calculate the average.

WA=((W1-W0)/W0)×100

W0: quality of the evaluation sample before water absorption (g)

W1: quality of the evaluation sample after water absorption (g)

<Evaluation of heat resistance> (glass transition temperature)

A test piece having a width of 5 mm and a length of 15 mm was cut into a test sample 3 by cutting the cured product for evaluation. Next, thermomechanical analysis was carried out by a tensile weighting method using a thermomechanical analyzer TMA-SS6100 (manufactured by Seiko Instruments Co., Ltd.). After the evaluation sample 3 was attached to the above apparatus, the measurement was continuously performed twice under the measurement conditions of a load of 1 G and a temperature increase rate of 5 ° C /min. The glass transition temperature is calculated from the point where the slope of the dimensional change signal of the second measurement changes, and the glass transition point temperature (° C.) is calculated. The coefficient of thermal expansion is an average linear thermal expansion coefficient (ppm/° C.) from 25 ° C to 150 ° C measured for the second time.

<Synthesis Example 1: Synthesis of acrylate compound having a cresol novolak structure and an epoxy group>

In 700 g of diethylene glycol monoethyl ether acetate, a cresol novolac type epoxy resin [manufactured by DIC, EPICLON N-660, epoxy equivalent 205] 2050 g (equivalent: 10.0), and acrylic acid 360 g were charged. (Equivalent: 5.0) and 1.5 g of hydroquinone were heated and stirred at 90 ° C to be uniformly dissolved. Connect Then, 5.9 g of triphenylphosphine was charged, and the mixture was heated to 120 ° C for 12 hours. The obtained reaction liquid was diluted with a solvent to obtain an acrylate compound (Product A).

‧Epoxy equivalent: 427

‧ Acid price: 0.49mgKOH/g

‧ Weight average molecular weight: 2000

‧ solid content of 65 mass% diethylene glycol monoethyl ether acetate solution

<Synthesis Example 2: Synthesis of a methacrylate compound having a bisphenol structure, a biscresol oxime structure, and an epoxy group>

In the reaction vessel, 20,000 g of a dixylenol type epoxy resin (YX4000 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185), bisphenol acetophenone (phenolic hydroxyl equivalent 145) 14 g, and biscresol oxime (JFE) were added. Manufactured by Chemical Co., Ltd., phenolic hydroxyl equivalent: 190) 170 g, and cyclohexanone 150 g, stirred and dissolved. Next, 0.5 g of a tetramethylammonium chloride solution was added dropwise, and the mixture was reacted under a nitrogen atmosphere at 180 ° C for 5 hours. Next, the temperature was lowered to 60 ° C, and 100 parts of isocyanate ethyl methacrylate (manufactured by Showa Denko Co., Ltd., trade name Karenz MOI, methacrylic acid equivalent 155) and dibutyltin dilaurate were dropped through a dropping funnel. After the completion of the dropwise addition, 0.04 parts of the mixed solution was allowed to stand at 70 ° C for 4 hours to cause the isocyanate group to disappear, whereby a methacrylate compound was obtained. After completion of the reaction, the mixture was filtered using a filter cloth, and diluted with a solvent to obtain a methacrylate compound (Production B).

‧Epoxy equivalent: 6400

‧ Acid price: 0.73mgKOH/g

‧ Weight average molecular weight: 29000

‧ solid content of 25% by mass of 1:1 solution of MEK and cyclohexanone

<Examples 1 to 3, Comparative Example 1>

The components were blended in the proportions as shown in Table 1, and the resin varnish was prepared by kneading using a triaxial roll. Next, the related resin varnish was uniformly coated and dried on a 16 mm thick polyethylene terephthalate film (R310-16B, manufactured by Mitsubishi Resin Co., Ltd., trade name) via a die coater. A photosensitive film with a support having a resin composition layer of 20 mm was obtained. Drying was carried out using a hot air convection dryer at 75 to 120 ° C (average 100 ° C) for 4.5 minutes. The measurement results and evaluation results of these are shown in Table 1.

The materials used are as follows.

(A) Ingredients Epoxy resin

‧HP-7200H (made by DIC): dicyclopentadiene type epoxy resin, epoxy equivalent 280, non-volatile 65% solvent oil solution

‧HP4032SS (DIC system): liquid naphthalene epoxy resin, epoxy equivalent 144

‧ZX1059 (Nippon Steel Chemical Co., Ltd.): 1:1 mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent 169

‧YX4000HK (Mitsubishi Chemical Co., Ltd.): crystalline 2-functional epoxy resin, epoxy equivalent 185

‧NC3000L (Nippon Chemical Co., Ltd.): biphenyl type epoxy resin, epoxy equivalent 269

(B) Ingredients Active esters, cyanate esters, benzoxazines

‧HPC8000-65T (made by DIC): dicyclopentadiene type diphenol compound (polycyclopentadiene type diphenol compound) type active ester hardener, solid part 65% toluene solution

‧BA230S75 (manufactured by Lonza Japan Co., Ltd.): a prepolymer of bisphenol A dicyanate, a MEK solution having a cyanate equivalent of about 232 and a nonvolatile content of 75% by mass.

‧ PT30S (manufactured by Lonza Japan Co., Ltd.): MEK solution of phenol novolac type polyfunctional cyanate resin cyanate equivalent of about 133 and nonvolatile content of 85% by mass

‧P-d benzoxazine (manufactured by Shikoku Chemical Co., Ltd.): benzoxazine monomer equivalent 217, non-volatile 60% by mass MEK solution

(C) component (meth) acrylate containing compound

‧Product A is synthesized according to Synthesis Example 1.

‧Product B is synthesized according to Synthesis Example 2

‧DPHA (Nippon Chemical Co., Ltd.): dipentaerythritol hexapropylene Acid ester, acid value 0.5mgKOH/g

‧ZFR-1533H (manufactured by Nippon Kayaku Co., Ltd.): bisphenol F type epoxy acrylate, 68% diethylene glycol monoethyl ether acetate solution with acid anhydride, acid value 70 mgKOH/ g, weight average molecular weight: 14000

(D) component photopolymerization initiator

‧IC819 (made by BASF Japan): bis(2,4,6-trimethylbenzhydrazide)-phenylphosphine oxide

‧ OXE-01 (made by BASF Japan): 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzidine)]

(E) Ingredients

‧ SOC2 (Admatechs Co., Ltd.): spherical fused vermiculite with an anisine-based decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573"), with an average particle diameter of 0.5 mm

‧ SOC1 (Admatechs Co., Ltd.): spherical fused vermiculite with an anilino-based decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573"), average particle size 0.24 mm)

(F) component hardening accelerator

‧DMAP (made by Wako Pure Chemical Co., Ltd.): 4-dimethylaminopyridine, non-volatile 2% by mass MEK solution

‧Co(III) (Tokyo Chemical Co., Ltd.): Cobalt (III) acetamidine acetone, non-volatile 1% by mass MEK solution

‧2P4MZ (Shikoku Chemical Co., Ltd.): 2-phenyl-4-methylimidazole, non-volatile 5% by mass DMF solution

(G) component rubber particles

‧AC3816N (manufactured by Ganz Chemical Co., Ltd.): core-shell rubber particles

(H) component light sensitizer

‧DETX-S (Nippon Chemical Co., Ltd.): 2,4-diethylthioxanthone

(I) Ingredients Solvent

‧IP150 (solvent oil)

‧MEK (methyl ethyl ketone)

As is apparent from the results of Table 1, in the examples using the photosensitive resin composition of the present invention, a photosensitive resin composition having photosensitivity (resolution and developability) and excellent insulation reliability can be provided. Furthermore, dielectric properties or water resistance are also excellent. On the other hand, in Comparative Example 1, although photosensitive (analytical property and developability) were used, an acid anhydride-modified epoxy acrylate resin was used because the compound (B) was not blended, so that the insulating property was poor and the dielectric properties were The water resistance is also poor, so that it cannot be used as a resin composition for interlayer insulation.

Claims (18)

A photosensitive resin composition comprising: (A) an epoxy resin; (B) one or more hardenings 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. The photosensitive resin composition of claim 1, wherein the (A) epoxy resin is used in combination and contains an epoxy resin which is liquid at a temperature of 20 ° C and an epoxy resin which is solid at a temperature of 20 ° C. The photosensitive resin composition of claim 1, wherein the non-volatile content of the photosensitive resin composition is 100% by mass, and the content of the component (A) is from 3 to 50% by mass. The photosensitive resin composition of claim 1, wherein the non-volatile content of the photosensitive resin composition is 100% by mass, and the content of the component (B) is 1 to 30% by mass. The photosensitive resin composition of claim 1, wherein the component (C) comprises a polymer having a (meth) acrylate structure having a weight average molecular weight of 500 to 100,000. The photosensitive resin composition of claim 1, wherein the component (C) has an epoxy group. The photosensitive resin composition of claim 1, wherein the acid value of the component (C) is 20 mgKOH/g or less. The photosensitive resin composition of claim 1, wherein when the nonvolatile component of the photosensitive resin composition is 100% by mass, (C) is formed. The content of the fraction is 1 to 25% by mass. The photosensitive resin composition of claim 1, further comprising (D) a photopolymerization initiator. The photosensitive resin composition of claim 1, further comprising (E) an inorganic filler. In the photosensitive resin composition of claim 10, when the nonvolatile content of the photosensitive resin composition is 100% by mass, the content of the (E) inorganic filler is from 10 to 85% by mass. In the photosensitive resin composition of claim 10, when the nonvolatile content of the photosensitive resin composition is 100% by mass, the content of the (E) inorganic filler is 50 to 85% by mass. The photosensitive resin composition of claim 1, which is used for an interlayer insulating layer of a multilayer printed wiring board. The photosensitive resin composition of claim 1, wherein the cured product of the photosensitive resin composition has a dielectric tangent of 0.005 to 0.05. The photosensitive resin composition of claim 1, wherein the water absorption of the cured product of the photosensitive resin composition is 0.01 to 3%. A photosensitive film having a support, which comprises the photosensitive resin composition according to any one of claims 1 to 15. A multilayer printed wiring board having a cured product of the photosensitive resin composition according to any one of claims 1 to 15. A semiconductor device characterized by using the multilayer printed wiring board of claim 17.