KR102228718B1 - Photosensitive resin composition - Google Patents

Abstract

(A) epoxy resin, (B) active ester curing agent, cyanate ester curing agent and benzoxazine curing agent, which have photosensitivity, have excellent insulation reliability, and have physical properties suitable for the build-up layer (interlayer insulation layer) of a multilayer printed wiring board. It provides a photosensitive resin composition containing at least one curing agent selected from the group consisting of, and (C) a compound having a (meth)acrylate structure.

Description

Photosensitive resin composition {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.

In the conventional photosensitive resin composition, an alkali developing type is the mainstream, and in order to enable development, an acrylate containing an acid anhydride group or a carboxyl group has been used. However, since the acid anhydride group or carboxyl group is liable to be thermally deteriorated, sufficient physical properties cannot be obtained with the cured product using the acrylate. In the case of the acid anhydride group or carboxyl group, there is a limit to the formation of an insulating layer with high insulation reliability. there was.

So, for example, Patent Document 1 discloses a photosensitive resin composition for MEMS comprising a specific photo cationic polymerization initiator and a specific epoxy resin, the use of which is limited to MEMS applications, and insulation reliability is insufficient. Therefore, in particular, sufficient performance as a build-up layer of a multilayer printed wiring board could not be exhibited. In addition, Patent Document 2 discloses a photosensitive resin composition for a protective film of a printed wiring board for a semiconductor package, but the insulation reliability is not sufficient and its use is limited to a protective film. I couldn't show it.

Patent Document 1: Japanese Unexamined Patent Application Publication No. 2009-263544 Patent Document 2: International Publication No. 2010/026927

Accordingly, an object of the present invention is to provide a resin composition having photosensitivity, excellent insulation reliability, and having physical properties suitable for a build-up layer (interlayer insulating layer) of a multilayer printed wiring board.

The inventors of the present invention are at least one curing agent selected from the group consisting of (A) an epoxy resin, (B) an active ester curing agent, a cyanate ester curing agent, and a benzoxazine curing agent, and (C) a compound having a (meth)acrylate structure. By using the photosensitive resin composition containing, it discovered that the said subject can be solved, and came to complete this invention.

That is, the present invention includes the following contents.

(1) (A) epoxy resin,

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

(C) a compound having a (meth)acrylate structure

A photosensitive resin composition containing.

[2] (A) The photosensitive resin composition according to [1], wherein the epoxy resin includes a liquid epoxy resin at a temperature of 20°C and a solid epoxy resin at a temperature of 20°C.

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

[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 nonvolatile component of the photosensitive resin composition is 100% by mass.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the component (C) contains a polymer having a (meth)acrylate structure having a weight average molecular weight of 500 to 100000.

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

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

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

[9] (D) The photosensitive resin composition according to any one of [1] to [8], further containing a photoinitiator.

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

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

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

[13] The photosensitive resin composition according to any one of [1] to [12], which is 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 dielectric loss tangent of the cured product of the photosensitive resin composition is 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 with a support comprising the photosensitive resin composition according to any one of [1] to [15].

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

[18] A semiconductor device comprising the multilayer printed wiring board according to [17].

According to the present invention, it is possible to provide a resin composition having photosensitivity, excellent insulation reliability, and having physical properties suitable for a build-up layer of a multilayer printed wiring board. In addition, the photosensitive resin composition of the present invention can provide a build-up layer having excellent dielectric properties and suppressing power consumption, and can provide a build-up layer having excellent water resistance and heat resistance.

Hereinafter, the present invention will be described in detail based on its preferred embodiment.

[Photosensitive resin composition]

The photosensitive resin composition of the present invention comprises at least one curing agent selected from the group consisting of (A) an epoxy resin, (B) an active ester curing agent, a cyanate ester curing agent, and a benzoxazine curing agent, and (C) (meth)acrylate. It is characterized by containing a compound having a structure.

Hereinafter, 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.

Although it does not specifically limit as an epoxy resin, For example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a cyclopentadiene type epoxy resin, a trisphenol epoxy resin, Naphthol novolac epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type Epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, butadiene structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexanedimethanol type epoxy Resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, and the like. Epoxy resins may be used alone or in combination of two or more.

It is preferable that the epoxy resin contains an epoxy resin having two or more epoxy groups per molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups per molecule.

In addition, it is preferable to include a liquid epoxy resin (hereinafter referred to as "liquid epoxy resin") at a temperature of 20°C and a solid epoxy resin (hereinafter referred to as "solid epoxy resin") at a temperature of 20°C. . As the epoxy resin, a resin composition having excellent flexibility can be obtained by using a liquid epoxy resin and a solid epoxy resin together. Further, the breaking strength of the insulating layer formed by curing the resin composition is also improved.

The liquid epoxy resin is preferably a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, or a naphthalene type epoxy resin, and a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a naphthalene type epoxy resin Is more preferable. As a specific example of a liquid epoxy resin, DIC Corporation "HP4032", "HP4032D", "EXA4032SS", "HP4032SS" (naphthalene type epoxy resin), Mitsubishi Chemical Corporation "jER828EL" (bisphenol A type Epoxy resin), ``jER807'' (bisphenol F type epoxy resin), ``jER152'' (phenol novolac type epoxy resin), Shinnittetsu Chemical Co., Ltd. ``ZX1059'' (bisphenol A type epoxy resin and bisphenol F type epoxy Resin mixture), etc. are mentioned. As a 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 preferable. Liquid epoxy resins may be used alone or in combination of two or more.

As the solid epoxy resin, tetrafunctional naphthalene type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, biphenyl type epoxy resin, or naphthylene ether type An epoxy resin is preferable, a tetrafunctional naphthalene type epoxy resin, a biphenyl type epoxy resin, or a naphthylene ether type epoxy resin is more preferable, and a biphenyl type epoxy resin is still more preferable. As a specific example of a solid epoxy resin, "HP-4700", "HP-4710" (4-functional naphthalene-type epoxy resin), "N-690" (cresol novolac-type epoxy resin) manufactured by DIC Corporation, and "N -695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200H", "HP-7200K-65I" (dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3" , "HP6000" (naphthylene ether type epoxy resin), "EPPN-502H" manufactured by Nippon Kayaku Co., Ltd. (trisphenol epoxy resin), "NC7000L" (naphthol novolac epoxy resin), "NC3000H", "NC3000 ", "NC3000L", "NC3100" (biphenyl-type epoxy resin), "ESN475" (naphthol novolac-type epoxy resin) manufactured by Shinnittetsu Chemical Co., Ltd., "ESN485" (naphthol novolac-type epoxy resin), "YX4000H", "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. can be mentioned. In particular, "YX4000HK" (bixylenol-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC3000L" (biphenyl-type epoxy resin), "HP-7200H" manufactured by DIC Corporation (dicyclopentadiene-type epoxy resin) Resin) is preferred. Solid epoxy resin may be used individually by 1 type, and may use 2 or more types together.

As an epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used in combination, the quantity ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1:0.1 to 1:4 by mass ratio. Do. By setting the amount ratio of the liquid epoxy resin and the solid epoxy resin to this range, i) suitable adhesion can be obtained when used in the form of an adhesive film, and ii) sufficient flexibility can be obtained when used in the form of an adhesive film. It can be used, the handling property is improved, and effects such as iii) being able to obtain an insulating layer having sufficient breaking strength can be obtained. 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 in the range of 1:0.3 to 1:3.5 by mass ratio, more preferably, , The range of 1:0.6 to 1:3 is more preferable, and the range of 1:0.8 to 1:2.5 is particularly preferable.

The content of the epoxy resin is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 45% by mass, and 7% by mass to 35% by mass when the nonvolatile component in the photosensitive resin composition is 100% by mass. % Is more preferable, and 8 mass%-20 mass% are especially preferable.

The epoxy equivalent of the epoxy resin is preferably 50 to 3000, more preferably 80 to 2000, still more preferably 110 to 1000. By being in this range, the crosslinking density of a cured product is sufficient and an insulating layer excellent in heat resistance is formed. In addition, the epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

<(B) component>

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

-Active ester curing agent-

The active ester curing agent used in the photosensitive resin composition of the present invention can improve heat resistance, dielectric properties, and water resistance when used as a cured product, and is particularly excellent in dielectric properties and water resistance. Although there is no restriction|limiting in particular as an active ester hardening agent, A compound which has two or more active ester groups per molecule is preferable. As the active ester curing agent, compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are generally preferred. Is used.

From the viewpoint of improving the heat resistance when used as a cured product, the active ester curing agent is preferably an active ester compound obtained from a reaction product obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylate compound, and a hydroxy compound and/or a thiol compound. , An active ester compound obtained from a carboxylic acid compound and a hydroxy compound is more preferable, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is still more preferable. Further, an aromatic compound having two or more active ester groups in one molecule obtained from a reaction product obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group is even more preferable. In addition, the active ester curing agent is an aromatic compound obtained from a reaction product obtained by reacting a compound having at least two or more carboxylic acids in one molecule and an aromatic compound having a phenolic hydroxyl group, and two or more active esters in one molecule of the aromatic compound Aromatic compounds having groups are particularly preferred. In addition, the active ester compound may be linear or multi-branched. Further, if the compound having at least two or more carboxylic acids in one molecule is a compound containing an aliphatic chain, compatibility with the resin composition can be improved, and if a compound having an aromatic ring, heat resistance can be improved. Active ester curing agents may be used alone or in combination of two or more.

Examples of the carboxylic acid compound that can be used include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromelliic acid, and the like. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable, and isophthalic acid and terephthalic acid are more preferable from the viewpoint of improving heat resistance when a cured product is formed. As a thiocarboxylic acid compound, thioacetic acid, thiobenzoic acid, etc. are mentioned, for example.

As an example of a phenol compound or a naphthol compound, specifically, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, fluoroglucine, benzenetriol, dicyclopentadiene-type diphenol compound (polycyclopentadiene-type diphenol compound), phenol novolac, and the like. have.

Among them, from the viewpoint of improvement of 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, phlorogle Leucine, benzenetriol, dicyclopentadiene type diphenol compound (polycyclopentadiene type diphenol compound) and phenol novolac are preferable, and catechol, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadiene type diphenol compound (Polycyclopentadiene-type diphenol compound) and phenol novolac are more preferable, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxy Benzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene type diphenol compound (polycyclopentadiene type diphenol compound), phenol novolac are more preferable, and 1,5-dihydro Roxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenol compound (polycyclopentadiene-type diphenol compound) and phenol novolac are more preferable. , 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type diphenol compound (polycyclopentadiene type diphenol compound) More preferred, and a dicyclopentadiene-type diphenol compound (polycyclopentadiene-type diphenol compound) is particularly preferred. Specific examples of the thiol compound include benzene dithiol and triazine dithiol.

As an active ester curing agent containing a dicyclopentadiene-type diphenol condensation structure, more specifically, a compound represented by the following general formula (1) can be mentioned.

In Formula 1, two Rs are each independently a phenyl group or a naphthyl group. k represents 0 or 1. n is the average of the repeating units and is 0.05 to 2.5.

From the viewpoint of lowering the dielectric loss tangent and improving heat resistance, R is preferably a naphthyl group. It is preferable that k is 0. In addition, it is preferable that n is 0.25 to 1.5.

As the active ester curing agent, an active ester compound disclosed in Japanese Unexamined Patent Application Publication No. 2004-277460 may be used, or a commercially available active ester curing agent may be used. Examples of commercially available active ester curing agents include, specifically, an active ester curing agent containing a dicyclopentadiene-type diphenol condensed structure, an active ester curing agent containing a naphthalene structure, and an active ester curing agent containing an acetylated product of phenol novolac. , An active ester curing agent containing a benzoylated phenol novolac is preferable, and among them, an active ester curing agent containing a naphthalene structure, a dicyclopentadiene-type diphenol compound (polycyclopentadiene-type diphenol compound) structure is included. The active ester curing agent is more preferable. 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 Corporation). Examples of the active ester curing agent containing a naphthalene structure include EXB9416-70BK (manufactured by DIC Corporation), and as an active ester curing agent containing an acetylated product of phenol novolac, for example , DC808 (manufactured by Mitsubishi Chemical Corporation), and examples of the active ester curing agent containing a benzoylated product of phenol novolac include YLH1026 (manufactured by Mitsubishi Chemical Corporation). In particular, HPC8000-65T (active ester curing agent containing a dicyclopentadiene-type diphenol compound (polycyclopentadiene-type diphenol compound) structure) manufactured by DIC Corporation is preferable.

-Cyanate ester curing agent-

The cyanate ester curing agent used in the photosensitive resin composition of the present invention can improve heat resistance, dielectric properties, and water resistance when used as a cured product, and is particularly excellent in heat resistance. The cyanate ester curing agent is not particularly limited, but, for example, novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester curing agent, dicyclopentadiene type cyanate ester curing agent, bisphenol type (Bisphenol A type, bisphenol F type, bisphenol S type, etc.) Cyanate ester type curing agent, and prepolymers in which these are partially triazineized, etc. are mentioned. The weight average molecular weight of the cyanate ester curing agent is not particularly limited, but 500 to 4500 are preferable, and 600 to 3000 are more preferable. Specific examples of the cyanate ester curing agent include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2 ,6-dimethylphenylcyanate) 4,4'-ethylidenediphenyldicyanate, hexafluoro bisphenol 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-(methylethylidene))benzene, bis(4 -Polyfunctional cyanate resins derived from bifunctional cyanate resins such as cyanate phenyl) thioether and bis (4-cyanate phenyl) ether, phenol novolac, cresol novolac, dicyclopentadiene structure-containing phenol resin, etc. And prepolymers in which these cyanate resins are partially triazineized. These may be used alone or in combination of two or more. As a commercially available cyanate ester resin, a phenol novolak type polyfunctional cyanate ester resin (manufactured by Lonza Japan, PT30S) is a prepolymer in which part or all of the bisphenol A dicyanate is triazineized to form a trimer (Lonza Japan). Co., Ltd. product, BA230S75), a dicyclopentadiene structure containing cyanate ester resin (Lonza Japan Co., Ltd., DT-4000, DT-7000), etc. are mentioned. In particular, ``PT30S'' (phenol novolac-type polyfunctional cyanate ester resin), ``BA230S75'' (prepolymer in which part or all of the bisphenol A dicyanate is triazineized to become a trimer) manufactured by Ronza Japan Co., Ltd. is preferable. Do.

-Benzoxazine curing agent-

The benzoxazine curing agent used in the photosensitive resin composition of the present invention can improve heat resistance, dielectric properties, and water resistance when used as a cured product. The benzoxazine curing agent is not particularly limited, but specific examples include Fa-type benzoxazine, Pd-type benzoxazine (manufactured by Shikoku Kasei Co., Ltd.), HFB2006M (manufactured by Showa Co., Ltd.), and the like. In particular, Pd-type benzoxazine (manufactured by Shikoku Kasei Co., Ltd.) is preferred.

The active ester curing agent, the cyanate ester curing agent, and the benzoxazine curing agent as component (B) may be used singly or in combination of two or more. In particular, an active ester curing agent is preferable in that it can reduce the dielectric loss tangent and the water absorption rate.

The content of the component (B) is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and more preferably 5 to 20% by mass when the nonvolatile component of the photosensitive resin composition is 100% by mass. It is more preferable to include %.

<(C) component>

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

The compound having a (meth)acrylate structure is not limited to these, but examples include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate, ethylene glycol, and methoxy Mono or diacrylates of glycols such as tetraethylene glycol, polyethylene glycol, and propylene glycol, acrylamides such as N,N-dimethylacrylamide, and N-methyrolacrylamide, N,N-dimethylaminoethylacrylate, etc. Polyhydric alcohols such as aminoalkyl acrylates, trimethylolpropane, pentaerythritol, dipentaerythritol, or polyhydric acrylates of the adducts of ethylene oxide, propylene oxide or ε-caprolactone, phenoxy acrylate, Phenols such as phenoxyethyl acrylate, acrylates such as ethylene oxide or propylene oxide adducts thereof, epoxy acrylates derived from glycidyl ethers such as trimethylol propane triglycidyl ether, melamine acrylates, and / Or methacrylates corresponding to the above acrylates, etc. are mentioned. Among these, polyhydric acrylates or polyhydric methacrylates are preferable. For example, as trivalent acrylates or methacrylates, trimethyrolpropane tri(meth)acrylate, pentaerythritol tri(meth) )Acrylate, trimethyrolpropane EO added tri(meth)acrylate, glycerin PO added tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetrafurfuryl alcohol oligo(meth)acrylate, ethylcarbi Tololigo(meth)acrylate, 1,4-butanediololigo(meth)acrylate, 1,6-hexanediololigo(meth)acrylate, trimethyrolpropanoligo(meth)acrylate, pentaerythritololigo(meth)acrylate )Acrylate, tetramethyrolmethane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, N,N,N',N'-tetrakis(β-hydroxyethyl)ethyldiamine (meth) ) Acrylic acid esters, etc., and examples of trivalent or higher acrylates or methacrylates include tri(2-(meth)acryloyloxyethyl)phosphate, tri(2-(meth)acryloyloxypropyl) Phosphate, tri(3-(meth)acryloyloxypropyl)phosphate, tri(3-(meth)acryloyl-2-hydroxyloxypropyl)phosphate, di(3-(meth)acryloyl-2- Hydroxyloxypropyl)(2-(meth)acryloyloxyethyl)phosphate, (3-(meth)acryloyl-2-hydroxyloxypropyl)di(2-(meth)acryloyloxyethyl)phosphate Phosphoric acid tryester (meth)acrylate, etc. are mentioned. It is preferable that the component (C) has an epoxy group from the viewpoint of improving the crosslinking property of a cured product and improving water resistance and heat resistance. In particular, ``the acrylate compound having a cresol novolac structure and an epoxy group'' synthesized according to Synthesis Example 1, and the ``methacrylate compound having a bixylenol structure, a biscresol fluorene structure, and an epoxy group'' synthesized according to Synthesis Example 2 It is particularly preferred. Any one of these (meth)acrylate compounds may be used alone, or two or more may be used in combination.

Component (C) preferably contains a polymer having a (meth)acrylate structure having a weight average molecular weight of 500 to 100000, more preferably 700 to 70000, still more preferably 1000 from the viewpoint of improving resolution. To 50000, particularly preferably 1500 to 35000.

In addition, the weight average molecular weight in this invention is measured by gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by the GPC method is LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P/K- manufactured by Showa Denko Corporation as a column. 804L/K-804L can be calculated by using chloroform or the like as a mobile phase, measuring at a column temperature of 40°C, and using a calibration curve of standard polystyrene.

In the photosensitive resin composition of the present invention, in order to increase the insulation reliability, it is preferable to use a compound having no carboxyl group as the component (C), but the photosensitive resin composition of the present invention can have a carboxyl group to such an extent that it does not impair the insulation reliability. have. For example, the acid value of the component (C) is preferably 20 mg KOH/g or less, more preferably 10 mg KOH/g or less, even more preferably 5 mg KOH/g or less, and even more preferably 3 mg KOH/g or less. , 1 mg KOH/g or less is particularly preferred.

The content of the component (C) is preferably 1 to 25% by mass, and more preferably 5 to 15% by mass, when the nonvolatile component of the photosensitive resin composition is 100% by mass.

The photosensitive resin composition of the present invention can further contain the following components.

<(D) Photoinitiator>

In the photosensitive resin composition of the present invention, by further containing (D) a photopolymerization initiator, the resin composition can be efficiently photocured to obtain a cured product. (D) The photoinitiator is not particularly limited, but, for example, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[ (4-methylphenyl)methyl]-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1 -One, benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoyl ethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl )Phosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphinate, 4,4'-bis(diethylamino)benzophenone, 1-hydroxy-cyclohexyl-phenylketone, 2,2 -Dimethoxy-1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, etc. Alkylphenone-based photoinitiator, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and other acylphosphine oxide-based photopolymerization initiators, 1,2-octanedione, 1-[4-(phenylthio) Oxime ester type photoinitiators, such as -, 2-(O-benzoyl oxime), and a sulfonium salt type photoinitiator, etc. are mentioned. In particular, acylphosphine oxide photopolymerization initiators such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by BASF Japan, IC819), 1,2-octanedione, 1-[4- (Phenylthio)-, 2-(O-benzoyloxime)] (BASF Japan Co., Ltd. product, OXE-01) oxime ester type photoinitiators, etc. are preferable because of high sensitivity. The photoinitiators may be used alone or in combination of two or more.

(D) The blending amount of the photopolymerization initiator is, from the viewpoint of sufficiently photocuring the photosensitive resin composition to improve insulation reliability, when the nonvolatile component in the photosensitive resin composition is 100% by mass, the content is made 0.1% by mass or more. It is preferable, it is more preferable to set it as 0.2 mass% or more, and it is still more preferable to set it as 0.3 mass% or more. On the other hand, the blending amount of the photopolymerization initiator is preferably 2% by mass or less when the nonvolatile component in the photosensitive resin composition is 100% by mass from the viewpoint of preventing a decrease in dimensional stability due to excessive sensitivity, It is more preferable to set it as 1 mass% or less, and it is still more preferable to set it as 0.5 mass% or less.

<(E) Inorganic filler>

The photosensitive resin composition of the present invention can lower the thermal expansion coefficient by further containing the (E) inorganic filler. (E) As an inorganic filler, for example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, titanium Barium oxide, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Among these, amorphous silica, fused silica, hollow silica, crystalline silica, synthetic Silica such as silica is particularly suitable. As silica, spherical silica is preferable. These may be used alone or in combination of two or more. As a preferable commercially available spherical fused silica, "SOC2" and "SOC1" manufactured by Adomex Co., Ltd. are mentioned, for example.

(E) The average particle diameter of the inorganic filler is preferably 1 µm or less, more preferably 0.8 µm or less, still more preferably 0.6 µm or less, and 0.4 µm or less from the viewpoint of improvement of insulation reliability and improvement of photocurability. Even more desirable. On the other hand, from the viewpoint of preventing aggregation of the inorganic filler, (E) the average particle diameter of the inorganic filler is preferably 0.01 µm or more, and more preferably 0.05 µm or more. In addition, as inorganic fillers, in order to improve moisture resistance and dispersibility, silane coupling agents (epoxysilane coupling agents, aminosilane coupling agents, mercaptosilane coupling agents, etc.), titanate coupling agents, silazane compounds, etc. It is preferable that it is surface-treated with a surface treatment agent of. These may be used alone or in combination of two or more.

Examples of the epoxysilane coupling agent include glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3, 4-epoxycyclohexyl)ethyltrimethoxysilane, and the like. Examples of the aminosilane-based coupling agent include aminopropylmethoxysilane, aminopropyl triethoxysilane, and N-phenyl-3-aminopropyltri Methoxysilane, N-2 (aminoethyl) aminopropyl trimethoxysilane, etc. are mentioned. As a mercaptosilane type coupling agent, for example, mercaptopropyl trimethoxysilane, mercaptopropyl triethoxysilane, etc. Can be mentioned. These may be used alone or in combination of two or more. As a commercially available coupling agent, for example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercapto Propyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltri Methoxysilane) and the like.

As a titanate-based coupling agent, for example, butyl titanate dimer, titanium octylene glycolate, diisopropoxytitanium bis (triethanol aminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) ) Titanium, bis (dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra(2 -Ethylhexyl) titanate, tetraisopropylbis(dioctylphosphite) titanate, tetraoctylbis(ditridecylphosphite) titanate, tetra(2,2-diallyloxy methyl-1-butyl)bis( Ditridecyl) phosphite titanate, isopropyl trioctanoyl titanate, isopropyl tricumylphenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl dimetha Acrylisostearoyl titanate, isopropyltri(dioctylphosphate) titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris(dioctylpyrophosphate) titanate, isopropyltri(N-) And amide ethyl/aminoethyl) titanate. These may be used alone or in combination of two or more.

As a silazane compound, for example, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, octamethyltrisilazane, hexa(t-butyl)disila Zan, hexabutyldisilazane, hexaoctyldisilazane, 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldi Silazane, 1,3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3- Dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, hexaphenyldisilazane, dimethylaminotrimethylsilazane, trisilazane, cyclotrisilazane, 1,1,3,3,5,5-hexamethyl And cyclotrisilazane, and hexamethyldisilazane is particularly preferable. These may be used alone or in combination of two or more.

(E) As the inorganic filler, it is preferable to use an inorganic filler surface-treated with a silazane compound from the viewpoint of improving the dispersibility of the photosensitive resin composition. And after surface-treating with a silazane compound, further improvement of dispersibility can be aimed at by surface-treating with a silane coupling agent. The amount of the silazane compound used for the surface treatment is preferably 0.001% by mass to 0.3% by mass, and more preferably 0.005% by mass to 0.2% by mass based on 100% by mass of the inorganic filler. As a spherical fused silica surface-treated with hexamethyldisilazane, "SC2050" manufactured by Adomex Co., Ltd. is mentioned, for example. In addition, the amount of the silane coupling agent used for the surface treatment is preferably 0.1% by mass to 6% by mass, more preferably 0.2% by mass to 4% by mass, and 0.3% by mass to 3% by mass based on 100% by mass of the inorganic filler. It is more preferable to be.

(E) The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of an inorganic filler on a volume basis with a laser diffraction type particle size distribution measuring device, and setting the median diameter thereof as an average particle diameter. The measurement sample can be preferably used in which an inorganic filler is dispersed in water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring device, LA-500, LA-750, etc. manufactured by Horiba Sesakusho Co., Ltd. can be used.

(E) The content in the case of blending the inorganic filler is 10% by mass or more when the nonvolatile component in the photosensitive resin composition is 100% by mass from the viewpoint of reducing the linear thermal expansion coefficient of the cured product and preventing deformation of the cured product. It is preferable, 20 mass% or more is more preferable, 30 mass% or more is still more preferable, 40 mass% or more is still more preferable, and 50 mass% or more is especially preferable from the viewpoint of improving heat resistance. On the other hand, the content in the case of blending the (E) inorganic filler is 85% by mass when the nonvolatile component in the photosensitive resin composition is 100% by mass from the viewpoint of prevention of decrease in alkali developability and improvement of photocurability. It is preferable that it is below, it is more preferable that it is 75 mass% or less, and it is still more preferable that it is 65 mass% or less.

<(F) hardening accelerator>

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

(F) Although it does not specifically limit as a hardening accelerator, For example, an amine-type hardening accelerator, a guanidine-type hardening accelerator, an imidazole-type hardening accelerator, a phosphonium-type hardening accelerator, a metal-type hardening accelerator, etc. are mentioned. These may be used alone or in combination of two or more.

Although it does not specifically limit as an amine-type hardening accelerator, For example, trialkylamines, such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl ) Amine compounds such as phenol and 1,8-diazabicyclo (5.4.0)-undecene, and the like. These may be used alone or in combination of two or more.

Although it does not specifically limit as a guanidine-type hardening accelerator, For example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-thryl)guanidine, Dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabi Cyclo[4.4.0]deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethyl Biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tril) biguanide, etc. have. These may be used alone or in combination of two or more.

Although it does not specifically limit as an imidazole-type hardening accelerator, For example, 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-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium 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-phenylimidazol isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethyl Imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2- And imidazole compounds such as methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of an imidazole compound and an epoxy resin. These may be used alone or in combination of two or more.

Although it does not specifically limit as a phosphonium-type hardening accelerator, For example, triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenyl borate, n-butylphosphonium tetraphenyl borate, tetrabutylphosphonium decanoate , (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, and the like. 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 (excluding metal curing accelerators), it is preferable to use an amine curing accelerator and an imidazole curing accelerator, among which 4-dimethylaminopyridine, 2-phenyl- It is particularly preferred to use 4-methylimidazole. The content of the curing accelerator (excluding the metal curing accelerator) is preferably in the range of 0.005% by mass to 1% by mass, and 0.01% by mass to 0.08% by mass when the nonvolatile component in the photosensitive resin composition is 100% by mass. It is more preferable that it is the range of. If it is less than 0.005 mass %, hardening becomes slow and there exists a tendency for long hardening time to be required, and if it exceeds 1 mass %, the storage stability of a resin composition tends to fall.

Although it does not specifically limit as a metal-type hardening accelerator, For example, organometallic complexes or organometallic salts of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, are mentioned. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt(II)acetylacetonate and cobalt(III)acetylacetonate, organic copper complexes such as copper(II)acetylacetonate, and zinc(II)acetylacetonate. Organic zinc complexes, organic iron complexes such as iron(III)acetylacetonate, organic nickel complexes such as nickel(II)acetylacetonate, and organic manganese complexes such as manganese(II)acetylacetonate. Examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like. 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, it is preferable to use an organic cobalt complex, and in particular, it is preferable to use cobalt(III)acetylacetonate. The content of the metal-based curing accelerator is preferably in the range of 25 ppm to 500 ppm, and more preferably in the range of 30 ppm to 200 ppm when the total solid content of the photosensitive resin composition is 100% by mass. Do.

<(G) Organic filler>

When the photosensitive resin composition of the present invention further contains (G) an organic filler, the stress of the cured product can be relaxed, and the occurrence of cracks can be prevented when it is set as a cured product. (G) Examples of the organic filler include rubber particles, polyamide fine particles, silicone particles, and the like, and in the present invention, it is preferable to use rubber particles.

As the rubber particles, any rubber particles may be used as long as they are particles of a resin that has been chemically crosslinked to a resin exhibiting rubber elasticity and made insoluble and insoluble in an organic solvent. For example, acrylonitrile Butadiene rubber particles, butadiene rubber particles, acrylic rubber particles, and the like. As the rubber particles, specifically, XER-91 (manufactured by Nippon Kose Rubber Co., Ltd.), Starphylloid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (above, manufactured by Gantsu Kasei Co., Ltd.) Farral Lloyd EXL2655, EXL2602 (above, made by Kureha Chemical Co., Ltd.), etc. are mentioned, AC3816N (made by Gantsu Kasei Co., Ltd.) is preferable.

As the polyamide fine particles, any polyamide fine particles may be used as long as they are fine particles 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, and the like. . Specific examples of the polyamide fine particles include VESTOSINT 2070 (manufactured by Daiseru Hulus Co., Ltd.), SP500 (manufactured by Toray Corporation), and the like.

(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 diameter of the organic filler can be measured using a dynamic light scattering method. (G) The average particle diameter of the organic filler is, for example, uniformly dispersing the organic filler in a suitable organic solvent by ultrasonic or the like, and using a thick particle diameter analyzer (FPAR-1000; manufactured by Otsuka Corporation). , The particle size distribution of the organic filler is prepared on a mass basis, and the median diameter can be measured by making the average particle diameter.

(G) The content in the case of blending the organic filler is preferably 0.1% by mass to 6% by mass when the total solid content of the photosensitive resin composition is 100% by mass from the viewpoint of improvement in heat resistance and improvement in laser processability, It is more preferably 0.5% by mass to 4% by mass.

<(H) photosensitizer>

The photosensitive resin composition of the present invention, (H) as a photosensitizer, N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, Tertiary amines such as triethanolamine may be added, and photosensitizers such as pyrazones, anthracenes, coumarins, xanthones and thioxanes may be added. In the present invention, it is preferable to use thioxanes as a photosensitizer, and it is more preferable to use 2,4-diethyl thioxanthone. Any one of the photosensitizers may be used alone, or two or more of them may be used in combination.

<(I) Organic solvent>

The photosensitive resin composition of the present invention can adjust the varnish viscosity by further containing (I) an organic solvent. (I) Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl Glycol ethers such as carbitol, 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 Esters, such as esters, aliphatic hydrocarbons such as octane and decane, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. Among them, solvent naphtha and methyl ethyl ketone are preferable. These are 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 the coatability of the photosensitive resin composition.

<(J) Other additives>

(J) As other additives, for example, fine particles such as melamine and organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, colorants such as naphthalene black, hydroquinone , Phenothiadine, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc. Various additives, such as a flame retardant such as a compound, an antimony compound, a phosphorus compound, an aromatic condensed phosphate ester, and a halogen-containing condensed phosphate ester, and a thermosetting resin such as a phenolic curing agent, can be added.

The photosensitive resin composition of the present invention is appropriately mixed with the above (A) to (C) (and optionally also (D) to (J)), and, if necessary, three rolls, a ball mill, a bead mill, a sand mill. It can be produced as a resin varnish by kneading or stirring by a kneading means such as a super mixer or a stirring means such as a planetary mixer.

The use of the photosensitive resin composition of the present invention is not particularly limited, but a photosensitive film, a photosensitive film with a support, an insulating resin sheet such as prepreg, a circuit board (for a laminated board, a multilayer printed wiring board, etc.), a solder resist, an underfill material, a die It can be widely used in applications requiring a resin composition, such as a bonding material, a semiconductor sealing material, a hole filling resin, and a component embedding resin. Among them, it is suitable 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 used as an insulating layer), and in particular, a resin composition for an interlayer insulating layer (a multilayer having a cured product of a photosensitive resin composition as an interlayer insulating layer) Printed wiring board), a resin composition for plating formation (a multilayer printed wiring board in which plating is formed on a cured product of a photosensitive resin composition) can be preferably used.

<Photosensitive film>

The photosensitive resin composition of the present invention can be applied onto a supporting substrate in a resin varnish state, and dried in an organic solvent to form a resin composition layer to form a photosensitive film. Further, a photosensitive film formed in advance on a support may be laminated on a support substrate to be used. The photosensitive film of the present invention can be laminated on various supporting substrates. As the supporting substrate, substrates such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate are mainly mentioned.

<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 in which a resin composition layer is layered on a support. In other words, in the photosensitive film with a support, a layer of the photosensitive resin composition is formed on the support. As a support, a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a polyvinyl alcohol film, a triacetyl acetate film, etc. are mentioned, for example, and a polyethylene terephthalate film is especially preferable.

As a commercially available support, for example, the product names ``Alpan MA-410'', ``E-200C'' manufactured by Oji Seishi Co., Ltd., polypropylene films such as Shin-Etsu Film Co., Ltd., and product names manufactured by Teijin Corporation `` Polyethylene terephthalate films, such as PS series, such as "PS-25", etc. are mentioned, but are not limited to these. These supports are preferably coated with a release agent such as a silicone coating agent on the surface in order to facilitate removal of the resin composition layer. 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 this thickness is less than 5 μm, the support (supporting film) tends to be torn during peeling of the support performed before development. On the other hand, if the thickness exceeds 50 μm, the resolution at the time of exposure from the support is reduced. There is a tendency to deteriorate. Further, a support for a low fish eye is preferred. Here, a fish eye is a material in which a material is hot-melted, and when a film is produced by kneading, extrusion, biaxial stretching, casting, or the like, foreign matter, undissolved material, oxidation-degraded product, and the like of the material enter the film.

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

By protecting the resin composition layer side of the photosensitive film with a support with a protective film, it is possible to prevent adhesion of dust or the like to the surface of the resin composition layer and scratches. As the protective film, a film made of the same material as the above support can be used. Although the thickness of the protective film is not particularly limited, it is preferably in the range of 1 µm to 40 µm, more preferably in the range of 5 µm to 30 µm, and still more preferably in the range of 10 µm to 30 µm. When this thickness is less than 1 µm, the handling property of the protective film tends to decrease, and when it exceeds 40 µm, the inexpensive property tends to be inferior. Moreover, as for the protective film, it is preferable that the adhesive force of a resin composition layer and a protective film is small with respect to the adhesive force of a resin composition layer and a support body.

In the photosensitive film with a support of the present invention, according to a method known to those skilled in the art, for example, a resin varnish obtained by dissolving the photosensitive resin composition of the present invention in an organic solvent is prepared, and the resin varnish is applied on the support, followed by heating or hot air. It can be produced by drying the organic solvent by spraying or the like to form a resin composition layer. Specifically, first, after completely removing the bubbles of the photosensitive resin composition by a vacuum defoaming method or the like, the photosensitive resin composition is applied on the support, and the solvent is removed by a hot stove or a far-infrared ray furnace, followed by drying. Subsequently, if necessary, a photosensitive film with a support can be produced by laminating a protective film on the obtained resin composition layer. 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% by mass to 60% by mass of an organic solvent, drying at 80°C to 120°C for 3 minutes to 13 minutes I can make it. The amount of the organic solvent remaining in the resin composition layer is preferably 5% by mass or less, and more preferably 2% by mass or less with respect to the total amount of the resin composition layer, from the viewpoint of preventing diffusion of the organic solvent in the post-process. Do. A person skilled in the art can set appropriate and suitable drying conditions through a simple experiment. The thickness of the resin composition layer is preferably in the range of 5 µm to 500 µm, and is preferably in the range of 10 µm to 200 µm, from the viewpoint of improving handling properties and preventing the sensitivity and resolution inside the resin composition layer from deteriorating. It is more preferable to set it as a range, it is more preferable to set it as the range of 15 micrometers-150 micrometers, It is still more preferable to set it as a range from 20 micrometers to 100 micrometers, It is especially preferable to set it as a range from 20 micrometers to 60 micrometers .

As a method of applying the photosensitive resin composition, for example, gravure coating method, micro gravure coating method, reverse coating method, kiss reverse coating method, die coating method, slot die method, lip coating method, comma coating method, blade coating method, Roll coating method, knife coating method, curtain coating method, chamber gravure coating method, slot orifice method, spray coating method, dip coating method, and the like.

The photosensitive resin composition may be applied several times, may be applied once, or may be applied in combination of a plurality of different methods. Among them, a die coating method having excellent uniform coatability is preferred. In addition, in order to avoid contamination of foreign matter or the like, it is preferable to perform the coating process in an environment where foreign matter is less generated, such as in a clean room.

<Multilayer printed wiring board>

Next, an example at the time of manufacturing a multilayer printed wiring board using a photosensitive resin composition is described.

When the interlayer insulating layer is produced using the photosensitive resin composition of the present invention, advantages such as (1) the via opening can be performed collectively, and (2) the via positioning accuracy is superior to that of the laser opening can be obtained. have.

(Application and drying process)

The photosensitive resin composition is applied directly on the circuit board in the state of a resin varnish, and the organic solvent is dried to form a photosensitive film on the circuit board. 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. In addition, the circuit board here refers to a board in which a patterned conductor layer (circuit) is formed on one side or both sides of the substrate as described above. In addition, in a multilayer printed wiring board formed by alternately stacking a conductor layer and an insulating layer, a substrate in which one or both sides of the outermost layer of the multilayer printed wiring board is a patterned conductor layer (circuit) is also included in the circuit board referred to herein. . Further, the surface of the conductor layer may be subjected to roughening treatment in advance by blackening treatment, copper etching, or the like.

As the coating method, full-scale printing by screen printing is generally used, but any other means may be used as long as it is a coating method that can be applied uniformly. For example, spray coating method, hot melt coating method, bar coating method, applicator method, blade coating method, knife coating method, air knife coating method, curtain flow coating method, roll coating method, gravure coating method, offset printing method, dip Coating methods, brush coating, and other conventional coating methods can all be used. After application, dry with a hot stove or a far-infrared ray, if necessary. The drying conditions are preferably set at 80°C to 120°C for 3 minutes to 13 minutes. In this way, a photosensitive film is formed on the circuit board.

(Lamination process)

In addition, when using a photosensitive film with a support, the resin composition layer side is laminated on one side or both sides of a circuit board using a vacuum laminator. In the laminating process, when the photosensitive film with a support has a protective film, after removing the protective film, the photosensitive film and the circuit board are preheated as needed, and the resin composition layer is pressed and heated to the circuit board while pressing. In the photosensitive film of the present invention, a method of laminating a circuit board under reduced pressure by a vacuum lamination method is preferably used.

The conditions of the lamination process 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 to 11 kgf/cm 2 (9.8×10) ⁴ N/m 2 to 107.9×10 ⁴ N/m 2 ), the pressing time is preferably 5 to 300 seconds, and the lamination is preferably performed under reduced pressure such that the air pressure is 20 mmHg (26.7 hPa) or less. In addition, the lamination process may be a batch type or may be a continuous type using a roll. The vacuum lamination method can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum applicator manufactured by Nichigo Morton, a vacuum pressurized laminator manufactured by Meiki Sesakusho, a roll-type dry coater manufactured by Hitachi Industries, and Hitachi AIC Manufacturing vacuum laminators, etc. are mentioned. In this way, a photosensitive film is formed on the circuit board.

(Exposure process)

After the photosensitive film is formed on the circuit board by a coating and drying process or a lamination process, an exposure process of irradiating a predetermined portion of the resin composition layer with active light through a mask pattern and photocuring the resin composition layer of the irradiation portion is performed. Conduct. Examples of the active light include ultraviolet rays, visible rays, electron rays, and X rays, and ultraviolet rays are particularly preferable. The irradiation amount of ultraviolet rays is generally 10mJ/cm2 to 1000mJ/cm2. The exposure method includes a contact exposure method in which a mask pattern is brought into close contact with a printed wiring board, and a non-contact exposure method in which light is exposed using a parallel light beam without being brought into close contact, and either of them may be used. Moreover, when a support body exists on a resin composition layer, you may expose from the support body, and you may expose the support body after peeling.

(Development process)

After the exposure process, when a support is present on the resin composition layer, a pattern can be formed by removing the support and then removing and developing the unphotocured portion (unexposed portion) by wet development or dry development. .

In the case of the wet development, as the developer, a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, which is safe, stable, and has good operability, is used, and in the present invention, among them, a developing step using an organic solvent is preferred. In addition, as the developing method, known methods such as spraying, shaking immersion, brushing, and scraping are suitably employed.

The organic solvent used as a developer is, for example, acetone, ethyl acetate, alkoxy ethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether.

It is preferable that the concentration of such an organic solvent is 2% by mass to 90% by mass based on the total amount of the developer. In addition, the temperature of such an organic solvent can be adjusted according to developability. In addition, these organic solvents 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, methylisobutyl ketone, γ- Butyrolactone and propylene glycol 1-monomethyl ether 2-acetate (PGMEA) are mentioned. Among them, PGMEA is preferable in the present invention.

In the pattern formation of the present invention, if necessary, two or more of the above-described developing methods may be used in combination. The development method includes a dip method, a paddle method, a spray method, a high pressure spray method, brushing, slapping, and the like, and a high pressure spray method is suitable for improving resolution. The spray pressure in the case of employing the spray method is preferably 0.05 MPa to 0.3 MPa.

(Post bake process)

After completion of the developing process, a post-baking process is performed to form an insulating layer (cured product). As a post-baking process, an ultraviolet irradiation process with a high-pressure mercury lamp, a heating process using a clean oven, etc. are mentioned. In the case of irradiating ultraviolet rays, the irradiation amount can be adjusted as necessary, and irradiation can be performed with an irradiation amount of about 0.05 J/cm 2 to 10 J/cm 2, for example. In addition, heating conditions may be appropriately selected depending on the type and content of the resin component in the resin composition, but preferably in the range of 20 minutes to 180 minutes at 150°C to 220°C, more preferably at 160°C to 200°C for 30 minutes. It is selected from the range of minutes to 120 minutes.

(Plating process)

Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as a vapor deposition method, a sputtering method, and an ion plating method can be used. In the vapor deposition method (vacuum vapor deposition method), for example, a metal film can be formed on the insulating layer by placing a support in a vacuum container and heating and evaporating the metal. The sputtering method also includes, for example, placing a support in a vacuum container, introducing an inert gas such as argon, applying a DC voltage, colliding the ionized inert gas with the target metal, and forming a metal film on the insulating layer by the repelled metal. can do.

In the case of wet plating, the surface of the formed insulating layer is subjected to a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order to form an uneven anchor. The swelling treatment with 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 an alkali solution, and examples of the alkali solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securiganth P (Swelling Dip Securiganth P), Swelling Dip Securiganth SBU (Swelling Dip Securiganth SBU) manufactured by Atotech Japan, etc. I can. The roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60°C to 80°C for 10 minutes to 30 minutes. Examples of the oxidizing agent include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous sodium hydroxide solution, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, and the like. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. As a commercially available oxidizing agent, alkaline permanganic acid solutions, such as Concentrate Compact CP, Dosing Solution Securigans P, manufactured by Atotech Japan Co., Ltd. are mentioned, for example. The neutralization treatment with the neutralization liquid is performed by immersing in the neutralization liquid for 3 minutes to 10 minutes at 30°C to 50°C. As the neutralizing liquid, an acidic aqueous solution is preferable, and as a commercial item, Atotech Japan Co., Ltd. Reduction Solution Securigans P is mentioned.

Next, a conductor layer is formed by combining electroless plating and electrolytic plating. In addition, a plating resist having an inverse pattern with the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As a method of pattern formation after that, for example, a subtractive method, a semi-positive method, or the like known to those skilled in the art can be used.

<Semiconductor equipment>

A semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention. A semiconductor device can be manufactured by mounting a semiconductor chip at a conductive location of the multilayer printed wiring board of the present invention. The "conducting point" is "a part that transmits electric signals in a multilayer printed wiring board", and the place may be a surface, a buried point, or any place. In addition, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and a bumpless build-up layer ( BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

The photosensitive resin composition of the present invention can provide a resin composition having photosensitivity, excellent insulation reliability, and suitable physical properties for a build-up layer of a multilayer printed wiring board. In addition, it has excellent dielectric properties, water resistance, and heat resistance, and can provide a cured product suitable for development with an organic solvent. Hereinafter, these characteristics will be described in detail.

The dielectric loss tangent of the cured product of the photosensitive resin composition of the present invention can be measured by <Measurement of dielectric properties> described later. Specifically, the dielectric loss tangent can be measured using a cavity resonance perturbation method with a frequency of 5.8 GHz and a measurement temperature of 23°C. From the viewpoint of preventing heat generation at high frequency, reducing signal delay and signal noise, the dielectric loss tangent is preferably 0.05 or less, more preferably 0.04 or less, even more preferably 0.03 or less, even more preferably 0.02 or less, and 0.013 or less. It is particularly preferred. On the other hand, the lower limit of the dielectric loss tangent is not particularly limited, but is 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 the measurement method described in <Water resistance measurement> described later. The absorption rate is preferably 3% or less, more preferably 2% or less, even more preferably 1% or less, and furthermore 0.8% or less, from the viewpoint of prevention of occurrence of voids during manufacture of printed wiring boards and improvement of insulation reliability. desirable. On the other hand, the lower limit of the water absorption rate is not particularly limited, but 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 the measurement method described in <Evaluation of heat resistance> described later. As an index of heat resistance, it is preferable to employ a glass transition point from the viewpoint of preventing deterioration of the cured product when a heat history is applied to the cured product. It is preferable that the glass transition point is 110 degreeC or more. The upper limit of the glass transition point is not particularly limited, but it is preferably 300°C or less. In addition, in terms of preventing distortion of the printed wiring board, a coefficient of thermal expansion may be employed as an index of heat resistance. The coefficient of thermal expansion is preferably 10 to 30 ppm/°C.

Example

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, "part" means a mass part.

<Adjustment of the laminate for evaluation>

On the copper layer of a glass epoxy substrate on which a circuit was formed with a copper layer having a thickness of 18 mm, CZ8100 (a surface treatment agent containing an organic acid, manufactured by MEC Co., Ltd.) was used to harmonize. Next, the resin composition layer of the photosensitive film with a support obtained in Examples and Comparative Examples was brought into contact with the copper circuit surface, and laminated using a vacuum laminator (Nichigo Morton Co., Ltd., VP160), and the glass epoxy substrate And, a laminate in which the resin composition layer and the support were laminated in this order was prepared. The compression bonding conditions were: a compression temperature of 80°C, a compression pressure of 0.2 MPa, and a pressing time of 20 seconds after 20 seconds of air purge. The laminate was allowed to stand for at least 1 hour at room temperature, and from above the support of the laminate, a round hole pattern was used to form round holes having a diameter of 80 mm, using a pattern forming apparatus, and UV rays of 100 mJ/cm 2. Exposure was performed. After standing at room temperature for 30 minutes, the support was removed from the laminate. In the example, the entire surface of the resin composition layer on the laminate was developed by immersing in PGMEA (propylene glycol 1-monomethyl ether 2-acetate) at 30° C. as a developer, and then, the developer was wiped off, and an ultraviolet ray of 1 J/cm 2 Irradiation was carried out, and further heat treatment was performed at 190° C. for 60 minutes to form an insulating layer having an opening of 80 mm in diameter on the laminate. This was made into a laminate for evaluation.

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

<Adjustment of cured product for evaluation>

The resin composition layer of the photosensitive film with a support obtained in Examples and Comparative Examples was exposed to light with ultraviolet rays of 100 mJ/cm 2 and photocured. Thereafter, the entire surface of the resin composition layer was irradiated with ultraviolet rays of 1 J/cm 2, further subjected to heat treatment at 190° C. for 90 minutes to form an insulating layer. After that, the support was removed to obtain a cured product for evaluation.

<Measurement method and evaluation method>

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

<Evaluation of photosensitivity>

(Resolution)

As an evaluation of the resolution, the shape of the resist of the round holes of the evaluation laminate was observed with SEM (magnification: 1000 times), and evaluated according to the following criteria.

(Circle): The shape of a round hole is good, and there is no curling or peeling in a tilted state.

X: The shape of the round hole is widened by the development, and there is a curling or peeling off in a tilted state.

(Developability)

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

(Circle): There is no developing residue on the board|substrate of the round hole of 80 mm in diameter, and it is excellent in developed residue removal property.

X: There is a developing residue on the substrate having a round hole having a diameter of 80 mm, and the developing residue removal property is inferior.

<Evaluation of insulation reliability>

In the imide film on which the comb electrode (line/space = 15 microns/15 microns) was formed, the resin composition layer of the photosensitive film with a support obtained in Examples and Comparative Examples was brought into contact with the surface of the copper circuit, and a vacuum laminator (ni It was laminated using Chigo Morton Co., Ltd., VP160). The compression bonding conditions were carried out for 20 seconds after the air purge, at a compression temperature of 80°C, a compression pressure of 0.2 MPa, and a pressurization time of 20 seconds. The laminate was allowed to stand at room temperature for 1 hour or more, and exposure was performed with ultraviolet rays of 100 mJ/cm 2 from above the support of the laminate. After allowing to stand at room temperature for 30 minutes, the support was removed from the laminate. Then, 1 J/cm<2> of ultraviolet rays irradiation was performed, and it heat-processed at 190 degreeC and 60 minutes further, and this was made into the laminated body for evaluation. This laminate for evaluation was put in a high-temperature, high-humidity bath in an atmosphere of 130°C and 85% humidity, and a voltage of 3.3 V was charged, and a HAST test was performed in the bath for 100 hours. The insulation resistance value of the evaluation laminate after 100 hours was evaluated according to the following criteria.

○: 10 ⁸ Ω or more

×: 10 ⁸ Ω or less

<Measurement of dielectric properties>

(Genetic tangent)

The cured product for evaluation was cut out into a length of 80 mm and a width of 2 mm to obtain evaluation sample 1. For this evaluation sample 1, a dielectric loss tangent was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by a cavity resonance perturbation method using an HP8362B device manufactured by AGILENT TECHNOLOGIES. Two evaluation samples 1 were measured, and an average value was calculated.

<Measurement of water resistance>

(Absorption rate)

The cured product for evaluation was cut out in 5 cm squares to obtain evaluation sample 2. Subsequently, the mass of the evaluation sample 2 was measured, and the evaluation sample after mass measurement was put in boiling pure water, and left for 1 hour in a state in which the evaluation sample 2 was completely immersed. After that, the evaluation sample 2 was taken out, the moisture on the surface was sufficiently wiped off, the mass after absorption was weighed to 0.1 mg, and the water resistance WA (%) was determined by the following equation. Measurements were made for four evaluation samples 2, and an average value was calculated.

WA = ((W1-W0)/W0)×100

W0: mass of the evaluation sample before absorption (g)

W1: Weight of the evaluation sample after absorption (g)

<Evaluation of heat resistance>

(Glass transition temperature)

The cured product for evaluation was cut into a test piece having a width of 5 mm and a length of 15 mm to obtain an evaluation sample 3. Next, thermomechanical analysis was performed by a tensile weighting method using a thermomechanical analysis device TMA-SS6100 (manufactured by Seiko Instruments Co., Ltd.). After attaching the evaluation sample 3 to the apparatus, it was measured twice in succession under the measurement conditions of a load of 1 g and a temperature increase rate of 5°C/min. As for the glass transition temperature, the glass transition point temperature (°C) was calculated from the point at which the slope of the dimensional change signal in the second measurement was changed. The coefficient of thermal expansion calculated the average coefficient of linear thermal expansion (ppm/°C) from 25°C to 150°C in the second measurement.

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

In 700 g of diethylene glycol monoethyl ether acetate, cresol novolak type epoxy resin [manufactured by DIC Corporation, EPICLON N-660, epoxy equivalent 205] 2050 g (equivalent: 10.0), acrylic acid 360 g (equivalent: 5.0), and hydroquinone 1.5 g was poured, and heated and stirred at 90°C to dissolve uniformly. Then, 5.9 g of triphenylphosphine was injected, the temperature was raised to 120°C, and the reaction was carried out for 12 hours. The obtained reaction solution was diluted with a solvent to obtain an acrylate compound (Production A).

ㆍ Epoxy equivalent: 427

ㆍ Acid value: 0.49mg KOH/g

ㆍ Weight average molecular weight: 2000

ㆍ 65 mass% solid content diethylene glycol monoethyl ether acetate solution

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

To the reaction vessel, bixylenol type epoxy resin (YX4000 manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 185) 190 g, bisphenol acetophenone (phenolic hydroxyl group equivalent 145) 14 g, biscresol fluorene (manufactured by JFE Chemical Co., Ltd., phenol) 170 g of hydroxyl group equivalent (190) and 150 g of cyclohexanone were added, followed by stirring to dissolve. Then, 0.5 g of a tetramethylammonium ammonium chloride solution was added dropwise, and the reaction was carried out at 180°C for 5 hours in a nitrogen atmosphere. Next, the temperature was lowered to 60°C, and a mixture of 100 parts of isocyanate ethyl methacrylate (manufactured by Showa Denko Co., Ltd., brand name Karenz MOI methacrylic equivalent 155) and 0.04 parts of dibutyltin dilaurate were added dropwise through a dropping funnel. Then, after the dropwise addition, the reaction solution was maintained at 70° C. for 4 hours to thereby dissipate an isocyanate group to obtain a methacrylate compound. After completion of the reaction, it was filtered using a filter cloth and diluted with a solvent to obtain a methacrylate compound (Production B).

ㆍ Epoxy equivalent: 6400

ㆍ Acid value: 0.73mg KOH/g

ㆍ Weight average molecular weight: 29000

ㆍ A 1:1 solution of MEK and cyclohexanone with 25% by mass solid content

<Examples 1 to 3, Comparative Example 1>

Each component was blended in the blending ratio shown in Table 1, and kneaded using three rolls to prepare a resin varnish. Next, this resin varnish was evenly applied and dried on a 16 mm thick polyethylene terephthalate film (R310-16B, manufactured by Mitsubishi Jushi Corporation, brand name) with a die coater, and dried to obtain a photosensitive film with a support having a resin composition layer of 20 mm. Obtained. Drying was performed at 75 to 120°C (average 100°C) for 4.5 minutes using a hot air convection dryer. These measurement results and evaluation results are shown in Table 1.

The materials used are described below.

(A) component epoxy resin

ㆍ HP7200H (manufactured by DIC Co., Ltd.): Dicyclopentadiene type epoxy resin, epoxy equivalent 280, solvent naphtha solution of 65% non-volatile content

ㆍ HP4032SS (manufactured by DIC Co., Ltd.): liquid naphthalene-type epoxy resin, epoxy equivalent 144

ㆍ ZX1059 (manufactured by Shinnittetsu Chemical Co., Ltd.): 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent 169

ㆍ YX4000HK (manufactured by Mitsubishi Chemical Co., Ltd.): Crystalline bifunctional epoxy resin, epoxy equivalent 185

ㆍ NC3000L (manufactured by Nihon Kayaku Co., Ltd.): Biphenyl type epoxy resin, epoxy equivalent 269

(B) component active ester, cyanate ester, benzoxazine

ㆍ HPC8000-65T (manufactured by DIC Corporation): Dicyclopentadiene type diphenol compound (polycyclopentadiene type diphenol compound) type active ester curing agent, solid content 65% toluene solution

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

ㆍ PT30S (manufactured by Ronza Japan Co., Ltd.): MEK solution of phenol novolak type polyfunctional cyanate ester resin cyanate equivalent of about 133 and non-volatile content of 85% by mass

ㆍ P-d-type benzoxazine (manufactured by Shikoku Kasei Co., Ltd.): MEK solution of 217 benzoxazine monomer equivalent and 60% by mass of non-volatile content

(C) Component (meth)acrylate-containing compound

ㆍ Synthesis according to Preparation A Synthesis Example 1

ㆍ Synthesis according to Preparation B Synthesis Example 2

ㆍ DPHA (manufactured by Nihon Kayaku Co., Ltd.): dipentaerythritol hexaacrylate, acid value 0.5 mg KOH/g

ㆍ ZFR-1533H (manufactured by Nippon Kayaku Co., Ltd.): Bisphenol F type epoxy acrylate, 68% solid content of diethylene glycol monoethyl ether acetate solution, acid anhydride denatured, acid value 70 mg KOH/g, weight average molecular weight: 14000

(D) component photoinitiator

ㆍ IC819 (manufactured by BASF Japan Co., Ltd.): Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide

ㆍ OXE-01 (manufactured by BASF Japan Co., Ltd.): 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)

(E) component silica

ㆍ SOC2 (manufactured by Adomex Co., Ltd.): spherical fused silica surface-treated with a phenylamino silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter 0.5mm

ㆍ SOC1 (manufactured by Adomex Co., Ltd.): spherical fused silica surface-treated with phenylamino silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter 0.24mm)

(F) component hardening accelerator

DMAP (manufactured by Wako Pure Chemical Industries, Ltd.): 4-dimethylaminopyridine, MEK solution of 2% by mass of non-volatile content

ㆍ Co(III) (manufactured by Tokyo Kasei Co., Ltd.): Cobalt(III) acetylacetonate, MEK solution of 1% by mass of non-volatile content

ㆍ 2P4MZ (manufactured by Shikoku Kasei Co., Ltd.): 2-phenyl-4-methylimidazole, a DMF solution of 5% by mass of non-volatile matter

(G) component rubber particles

ㆍ AC3816N (manufactured by Gantsu Kasei Co., Ltd.): core-shell rubber particles

(H) component photosensitizer

ㆍ DETX-S (manufactured by Kayaku Co., Ltd. in Japan): 2,4-diethyl thioxanthone

(I) component solvent

ㆍ IP150 (solvent naphtha)

ㆍ MEK (methyl ethyl ketone)

From the results of Table 1, it was found that in the examples using the photosensitive resin composition of the present invention, a photosensitive resin composition having photosensitivity (resolution and developability) and excellent in insulation reliability can be provided. In addition, it has excellent dielectric properties and water resistance. On the other hand, in Comparative Example 1, it has photosensitivity (resolution and developability), but since the component (B) is not blended and an acid anhydride-modified epoxy acrylate resin is used, the insulation properties are poor, and dielectric properties and water resistance It also fell, and was not usable as a resin composition for interlayer insulation.

Claims (18)

(A) epoxy resin,
(B) at least one curing agent selected from the group consisting of an active ester curing agent, a cyanate ester curing agent and a benzoxazine curing agent,
(C) a compound having a (meth)acrylate structure, and
(E) inorganic filler
As a photosensitive resin composition containing,
When the nonvolatile component of the photosensitive resin composition is 100% by mass, (E) the content of the inorganic filler is 30% by mass or more,
When the nonvolatile component of the photosensitive resin composition is 100% by mass, the content of the component (C) is 1 to 25% by mass. The photosensitive resin composition according to claim 1, wherein (A) as the epoxy resin, a liquid epoxy resin at a temperature of 20°C and a solid epoxy resin at a temperature of 20°C are used in combination. The photosensitive resin composition according to claim 1, wherein when the nonvolatile component of the photosensitive resin composition is 100% by mass, the content of the component (A) is 3 to 50% by mass. The photosensitive resin composition according to claim 1, wherein when the nonvolatile component of the photosensitive resin composition is 100% by mass, the content of the component (B) is 1 to 30% by mass. The photosensitive resin composition according to claim 1, wherein the component (C) contains a polymer having a (meth)acrylate structure having a weight average molecular weight of 500 to 100000. The photosensitive resin composition according to claim 1, wherein the component (C) has an epoxy group. The photosensitive resin composition according to claim 1, wherein the acid value of the component (C) is 20 mg KOH/g or less. The photosensitive resin composition according to claim 1, further comprising (D) a photoinitiator. The photosensitive resin composition according to claim 1, wherein when the nonvolatile component of the photosensitive resin composition is 100% by mass, (E) the content of the inorganic filler is 50% by mass or more. The photosensitive resin composition according to claim 1, wherein when the nonvolatile component of the photosensitive resin composition is 100% by mass, (E) the content of the inorganic filler is 85% by mass or less. The photosensitive resin composition according to claim 1, which is for an interlayer insulating layer of a multilayer printed wiring board. 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. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition has a water absorption rate of 0.01 to 3% of the cured product. A photosensitive film with a support containing the photosensitive resin composition according to any one of claims 1 to 13. A multilayer printed wiring board comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 13. A semiconductor device using the multilayer printed wiring board according to claim 15. delete delete