JP7334820B2 - Photosensitive resin composition, photosensitive film with support, multilayer printed wiring board, and semiconductor device - Google Patents

Description

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

Conventional photosensitive resin compositions are predominantly of the alkaline development type, and have used acid anhydride group- or carboxyl group-containing acrylates to enable development. However, since acid anhydride groups and carboxyl groups are easily degraded by heat, sufficient physical properties cannot be obtained from cured products using the acrylate, and when acid anhydride groups and carboxyl groups are present, high insulation reliability There is a limit to the formation of an insulating layer having

Therefore, for example, Patent Document 1 discloses a photosensitive resin composition for MEMS containing a specific photocationic polymerization initiator and a specific epoxy resin, but its use is limited to MEMS use. However, since the insulating reliability is insufficient, it was not possible to exhibit sufficient performance as a build-up layer of a multilayer printed wiring board. In addition, Patent Document 2 discloses a photosensitive resin composition for a protective film of a printed wiring board for a semiconductor package, but the insulation reliability is not sufficient, and its application is limited to a protective film. Sufficient performance as a build-up layer of a printed wiring board could not be exhibited.

JP 2009-263544 A WO2010/026927

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

We have found (A) epoxy resins, (B) one or more curing agents selected from the group consisting of active ester curing agents, cyanate ester curing agents and benzoxazine curing agents, and (C) (meth) The inventors have found that the above problems can be solved by using a photosensitive resin composition containing a compound having an acrylate structure, and have completed the present invention.

That is, the present invention includes the following contents.
[1] (A) epoxy resin,
(B) one or more curing agents 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,
A photosensitive resin composition containing
[2] The photosensitive resin composition according to [1], wherein (A) an epoxy resin that is liquid at a temperature of 20°C and an epoxy resin that is solid at a temperature of 20°C are used in combination as the epoxy resin.
[3] The photosensitive resin composition according to [1] or [2], wherein the content of component (A) is 3 to 50% by mass when the non-volatile component of the photosensitive resin composition is 100% by mass.
[4] The photosensitive resin according to any one of [1] to [3], wherein the content of the component (B) is 1 to 30% by mass when the non-volatile component of the photosensitive resin composition is 100% by mass. Composition.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein component (C) contains a polymer having a (meth)acrylate structure with a weight average molecular weight of 500 to 100,000.
[6] The photosensitive resin composition according to any one of [1] to [5], wherein component (C) has an epoxy group.
[7] The photosensitive resin composition according to any one of [1] to [6], wherein component (C) has an acid value of 20 mgKOH/g or less.
[8] The photosensitive resin according to any one of [1] to [7], wherein the content of the component (C) is 1 to 25% by mass when the non-volatile component of the photosensitive resin composition is 100% by mass. Composition.
[9] The photosensitive resin composition according to any one of [1] to [8], further comprising (D) a photopolymerization initiator.
[10] The photosensitive resin composition according to any one of [1] to [9], which further contains (E) an inorganic filler.
[11] The photosensitive resin composition according to [10], wherein the content of the inorganic filler (E) is 10 to 85% by mass when the non-volatile component of the photosensitive resin composition is 100% by mass.
[12] The photosensitive resin composition according to [10], wherein the content of the inorganic filler (E) is 50 to 85% by mass when the non-volatile 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 used as 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 loss tangent of 0.005 to 0.05.
[15] The photosensitive resin composition according to any one of [1] to [14], wherein the cured product of the photosensitive resin composition has a water absorption of 0.01 to 3%.
[16] A support-attached photosensitive film comprising the photosensitive resin composition according to any one of [1] to [15].
[17] A multilayer printed wiring board comprising 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 physical properties suitable for a buildup layer of a multilayer printed wiring board. Furthermore, the photosensitive resin composition of the present invention can provide a buildup layer with excellent dielectric properties and reduced power consumption, and can provide a buildup layer with excellent water resistance and heat resistance. can.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention comprises (A) an epoxy resin, (B) one or more curing agents 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.

Components (A) to (C) contained in the resin composition of the present invention are described below.

<(A) Component>
(A) Component is an epoxy resin.

Examples of epoxy resins include, but are not limited to, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol epoxy resin. Resin, naphthol novolak epoxy resin, phenol novolak epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, cresol Novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naphthyl Lene ether type epoxy resins, trimethylol type epoxy resins, and the like can be mentioned. An epoxy resin may be used individually by 1 type, or may use 2 or more types together.

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 mass %, at least 50 mass % or more of the epoxy resin preferably has two or more epoxy groups in one molecule.

In addition, it is preferable to contain an epoxy resin that is liquid at a temperature of 20° C. (hereinafter referred to as “liquid epoxy resin”) and an epoxy resin that is solid at a temperature of 20° C. (hereinafter referred to as “solid epoxy resin”). . By using both a liquid epoxy resin and a solid epoxy resin as epoxy resins, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the insulating layer formed by curing the resin composition is also improved.

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, or naphthalene type epoxy resin is preferable, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, or naphthalene type epoxy resin is preferable. more preferred. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", "EXA4032SS" and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation, and "jER828EL" (bisphenol A manufactured by Mitsubishi Chemical Corporation). type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "ZX1059" manufactured by Nippon Steel Chemical Co., Ltd. (bisphenol A type epoxy resin and bisphenol F type epoxy resin resin mixtures) and the like. 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. A liquid epoxy resin may be used individually by 1 type, or 2 or more types may be used together.

Solid epoxy resins include tetrafunctional naphthalene type epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol epoxy resin, naphthol novolak epoxy resin, biphenyl type epoxy resin, and naphthylene ether type epoxy resin. Preferred are tetrafunctional naphthalene type epoxy resins, biphenyl type epoxy resins, and naphthylene ether type epoxy resins, and even more preferred are biphenyl type epoxy resins. Specific examples of solid epoxy resins include "HP-4700" and "HP-4710" (tetrafunctional naphthalene type epoxy resin), "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation, " N-695" (cresol novolac type epoxy resin), "HP7200", "HP7200H", "HP7200K-65I" (dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "HP6000" (naphthylene ether type epoxy resin), Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol epoxy resin), "NC7000L" (naphthol novolac 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 novolac type epoxy resin), "YX4000H" manufactured by Mitsubishi Chemical Corporation, "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin), and the like. In particular, "YX4000HK" (bixylenol type epoxy resin) and "NC3000L" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. and "HP7200H" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation are preferable. . Solid epoxy resins may be used singly or in combination of two or more.

When a liquid epoxy resin and a solid epoxy resin are used together as epoxy resins, the ratio by mass (liquid epoxy resin: solid epoxy resin) is in the range of 1:0.1 to 1:4. preferable. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin in such a range, i) moderate adhesiveness is provided when used in the form of an adhesive film, and ii) when used in the form of an adhesive film. Effects such as obtaining sufficient flexibility, improving handleability, and iii) obtaining an insulating layer having sufficient breaking strength can be obtained. From the viewpoint of the above effects i) to iii), the ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is 1:0.3 to 1:3.5 by mass. is more preferred, the range of 1:0.6 to 1:3 is more preferred, and the range of 1:0.8 to 1:2.5 is particularly preferred.
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. % by mass is more preferred, and 8 to 20% by mass is particularly preferred.

The epoxy equivalent of the epoxy resin is preferably 50-3000, more preferably 80-2000, still more preferably 110-1000. Within this range, the crosslink density of the cured product is sufficient, resulting in an insulating layer with excellent heat resistance. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing one equivalent of epoxy groups.

<(B) Component>
Component (B) is one or more curing agents selected from the group consisting of active ester curing agents, cyanate ester curing agents and benzoxazine curing agents.

- Active ester curing agent -
The active ester curing agent used in the photosensitive resin composition of the present invention can improve the heat resistance, dielectric properties and water resistance of the cured product, and is particularly excellent in dielectric properties and water resistance. The active ester curing agent is not particularly limited, but compounds having two or more active ester groups in one molecule are preferred. Active ester curing agents generally include 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. It is preferably used.

From the viewpoint of improving the heat resistance of the cured product, the active ester curing agent is obtained from a reaction product obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. An active ester compound is preferred, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is more preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is even more preferred. Further, an aromatic compound having two or more active ester groups in one molecule obtained from a reactant obtained by reacting a carboxylic acid compound and an aromatic compound having a phenolic hydroxyl group is even more preferable. The active ester curing agent is an aromatic compound obtained from a reactant 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 An aromatic compound having two or more active ester groups in one molecule of the aromatic compound is particularly preferred. Also, 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, the compatibility with the resin composition can be enhanced, and if the compound has an aromatic ring, the heat-resistant can increase the quality. The active ester curing agent may be used singly or in combination of two or more.

Carboxylic acid compounds that can be used include, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, and isophthalic acid and terephthalic acid are more preferred, from the viewpoint of improving the heat resistance of the cured product. Examples of thiocarboxylic acid compounds include thioacetic acid and thiobenzoic acid.

Specific examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, 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, tetra Hydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene-type diphenol compound (polycyclopentadiene-type diphenol compound), phenol novolak, and the like.

Among them, 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, phloroglucine, benzenetriol, dicyclopentadiene type diphenol Compounds (polycyclopentadiene-type diphenol compounds), phenol novolacs are preferred, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone , phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds (polycyclopentadiene-type diphenol compounds), phenol novolacs, and more preferably 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxy naphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene-type diphenol compound (polycyclopentadiene-type diphenol compound), phenol novolak are more preferred, and 1,5-dihydroxynaphthalene, 1,6-dihydroxy Naphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenol compound (polycyclopentadiene-type diphenol compound), and phenol novolac are more preferable, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 ,6-dihydroxynaphthalene and dicyclopentadiene-type diphenol compounds (polycyclopentadiene-type diphenol compounds) are particularly preferred, and dicyclopentadiene-type diphenol compounds (polycyclopentadiene-type diphenol compounds) are particularly preferred. Specific examples of thiol compounds include benzenedithiol and triazinedithiol.

Active ester curing agents containing a dicyclopentadiene-type diphenol condensation structure include, more specifically, compounds represented by the following formula (1).

In formula (1), two R's are each independently a phenyl group or a naphthyl group. k represents 0 or 1; n is 0.05 to 2.5 on average for repeating units.

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

As the active ester curing agent, an active ester compound disclosed in Japanese Patent Application Laid-Open No. 2004-277460 may be used, and a commercially available active ester curing agent may also be used. Examples of commercially available active ester curing agents include, specifically, an active ester curing agent containing a dicyclopentadiene type diphenol condensation structure, an active ester curing agent containing a naphthalene structure, and an active ester curing agent containing an acetylated phenol novolac. Ester curing agents and active ester curing agents containing benzoylated phenol novolak are preferred, and among them, active ester curing agents containing a naphthalene structure and dicyclopentadiene type diphenol compounds (polycyclopentadiene type diphenol compound) structures are preferred. Active ester curing agents are more preferred. Active ester curing agents containing a dicyclopentadiene-type diphenol compound (polycyclopentadiene-type diphenol compound) structure include, for example, EXB9451, EXB9460, EXB9460S, and HPC8000-65T (manufactured by DIC Corporation). Active ester curing agents containing a naphthalene structure include, for example, EXB9416-70BK (manufactured by DIC Corporation), and active ester curing agents containing acetylated phenol novolacs include, for example, DC808 (Mitsubishi Chemical Corporation (manufactured by Mitsubishi Chemical Corporation), and examples of the active ester curing agent containing a benzoylated phenol novolak include YLH1026 (manufactured by Mitsubishi Chemical Corporation). In particular, HPC8000-65T (an 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 the heat resistance, dielectric properties and water resistance of the cured product, and is particularly excellent in heat resistance. The cyanate ester curing agent is not particularly limited. , bisphenol F-type, bisphenol S-type, etc.) cyanate ester-based curing agents, and prepolymers obtained by partially triazinizing these. The weight average molecular weight of the cyanate ester curing agent is not particularly limited, but is preferably 500-4500, more preferably 600-3000. Specific examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate (oligo(3-methylene-1,5-phenylenecyanate)), 4,4′-methylenebis(2,6-dimethylphenylcyanate). , 4,4′-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3 ,5-dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, bifunctional cyanate such as bis(4-cyanatophenyl)ether Polyfunctional cyanate resins derived from resins, phenol novolac, cresol novolac, dicyclopentadiene structure-containing phenol resins, etc., and prepolymers obtained by partially triazine-forming these cyanate resins. These may be used singly or in combination of two or more. Examples of commercially available cyanate ester resins include phenol novolak type polyfunctional cyanate ester resin (PT30S, manufactured by Lonza Japan Co., Ltd.), and a prepolymer in which part or all of bisphenol A dicyanate is triazined to form a trimer ( BA230S75, manufactured by Lonza Japan Co., Ltd.), dicyclopentadiene structure-containing cyanate ester resins (DT-4000, DT-7000, manufactured by Lonza Japan Co., Ltd.), and the like. In particular, "PT30S" (phenol novolac type polyfunctional cyanate ester resin) and "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazined to form a trimer) manufactured by Lonza Japan Co., Ltd. are preferable. .

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

The active ester curing agent, the cyanate ester curing agent, and the benzoxazine curing agent, which are components (B), may be used alone or in combination of two or more. In particular, an active ester curing agent is preferred because it can reduce dielectric loss tangent and water absorption.
The content of the component (B) is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, more preferably 5 to 20% by mass, when the nonvolatile component of the photosensitive resin composition is 100% by mass. % is more preferable.

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

Examples of compounds having a (meth)acrylate structure include, but are not limited to, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate, ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol. mono- or diacrylates of glycols such as N,N-dimethylacrylamide, acrylamides such as N-methylolacrylamide, aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate, trimethylolpropane, pentaerythritol, dipenta Polyhydric alcohols such as erythritol or polyhydric acrylates of adducts of these with ethylene oxide, propylene oxide or ε-caprolactone, phenols such as phenoxy acrylate and phenoxyethyl acrylate, or acrylates such as ethylene oxide or propylene oxide adducts thereof , epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether, melamine acrylates, and/or methacrylates corresponding to the above acrylates. Among these, polyvalent acrylates or polyvalent methacrylates are preferable. For example, trivalent acrylates or methacrylates include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane EO-added tri(meth)acrylate, glycerin PO-added tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetrafurfuryl alcohol oligo(meth)acrylate, ethyl carbitol oligo(meth)acrylate, 1,4-butanediol Oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate ) acrylates, N,N,N′,N′-tetrakis(β-hydroxyethyl)ethyldiamine (meth)acrylic acid esters, and 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) Phosphoric acid triester (meth)acrylates such as acryloyloxyethyl)phosphate may be mentioned. The component (C) preferably has an epoxy group from the viewpoint of improving the crosslinkability of the cured product and improving the 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 are particularly preferred. Any one of these (meth)acrylate compounds may be used alone, or two or more thereof may be used in combination.

Component (C) preferably contains a polymer having a (meth)acrylate structure with a weight average molecular weight of 500 to 100,000, more preferably 700 to 70,000, and even more preferably 1,000 to 50,000, from the viewpoint of improving resolution. It is preferably 1,500 to 35,000.

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

In the photosensitive resin composition of the present invention, in order to improve the insulation reliability, it is preferable to use a compound having no carboxyl group as the component (C). It can have a carboxyl group to the extent that it does not interfere with the properties. For example, the acid value of component (C) is preferably 20 mgKOH/g or less, more preferably 10 mgKOH/g or less, even more preferably 5 mgKOH/g or less, even more preferably 3 mgKOH/g or less, and particularly preferably 1 mgKOH/g or less.

The content of component (C) is preferably 1 to 25% by mass, more preferably 5 to 15% by mass, based on 100% by mass of non-volatile components in the photosensitive resin composition.

The following components can be further added to the photosensitive resin composition of the present invention.

<(D) Photoinitiator>
By further including (D) a photopolymerization initiator in the photosensitive resin composition of the present invention, the resin composition can be efficiently photocured to form a cured product. (D) The photopolymerization initiator is not particularly limited, but examples include 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-morpholinopropan-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 and other alkylphenone-based photopolymerization initiators, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide Acylphosphine oxide-based photopolymerization initiators such as, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)] and other oxime ester-based photopolymerization initiators, A sulfonium salt-based photopolymerization initiator and the like are included. In particular, acylphosphine oxide photopolymerization initiators such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by BASF Japan Ltd., IC819), 1,2-octanedione, 1-[4 -(Phenylthio)-,2-(O-benzoyloxime)] (OXE-01, manufactured by BASF Japan Ltd.) and other oxime ester photopolymerization initiators are preferred due to their high sensitivity. Any one of the photopolymerization initiators may be used alone, or two or more thereof may be used in combination.

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

<(E) Inorganic filler>
The thermal expansion coefficient of the photosensitive resin composition of the present invention can be reduced by further containing (E) an inorganic filler. (E) Inorganic fillers include, 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, etc. Among them, amorphous silica, fused silica, hollow silica, crystalline silica, Silica, such as synthetic silica, is particularly preferred. Spherical silica is preferable as silica. These may be used singly or in combination of two or more. Preferred commercially available spherical fused silicas include “SOC2” and “SOC1” manufactured by Admatechs Co., Ltd., for example.

(E) The average particle diameter of the inorganic filler is preferably 1 μm or less, more preferably 0.8 μm or less, and 0.6 μm or less from the viewpoint of improving insulation reliability and improving photocurability. It is more preferably 0.4 μm or less, and even more preferably 0.4 μm or less. On the other hand, the average particle diameter of the (E) inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, from the viewpoint of preventing aggregation of the inorganic filler. As inorganic fillers, silane coupling agents (epoxysilane coupling agents, aminosilane coupling agents, mercaptosilane coupling agents, etc.) and titanate coupling agents are used to improve moisture resistance and dispersibility. , silazane compounds, and other surface-treating agents are preferred. These may be used singly or in combination of two or more.

Examples of epoxysilane coupling agents include glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, and (3,4-epoxycyclohexyl). ethyltrimethoxysilane and the like, and aminosilane-based coupling agents include, for example, aminopropylmethoxysilane, aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2(aminoethyl)amino propyltrimethoxysilane and the like, and examples of mercaptosilane-based coupling agents include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, and the like. These may be used singly or in combination of two or more. Examples of commercially available coupling agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. ), Shin-Etsu Chemical Co., Ltd. “KBE903” (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane), and the like.

Examples of titanate-based coupling agents include butyl titanate dimer, titanium octylene glycolate, diisopropoxytitanium bis(triethanolamine), dihydroxytitanium bislactate, dihydroxybis(ammonium lactate) titanium, and bis(dioctylpyrophosphate)ethylene. Titanate, bis(dioctylpyrophosphate)oxyacetate titanate, tri-n-butoxy titanium monostearate, tetra-n-butyl titanate, tetra(2-ethylhexyl) titanate, tetraisopropylbis(dioctylphosphite)titanate, tetraoctylbis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyl trioctanoyl titanate, isopropyl tricumylphenyl titanate, isopropyl triisostearoyl titanate, isopropyl isopropyl stearoyl diacryl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tri(dioctylphosphate) titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tri(N-amidoethyl/aminoethyl) titanate, etc. be done. These may be used singly or in combination of two or more.

Examples of silazane compounds include hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, octamethyltrisilazane, hexa(t-butyl)disilazane, hexabutyldisilazane, hexa octyldisilazane, 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1, 3-diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, hexaphenyldisilazane, dimethyl Aminotrimethylsilazane, trisilazane, cyclotrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane and the like can be mentioned, and hexamethyldisilazane is particularly preferred. These may be used singly or in combination of two or more.

(E) The inorganic filler is preferably an inorganic filler surface-treated with a silazane compound from the viewpoint of improving the dispersibility of the photosensitive resin composition. Further dispersibility can be improved by surface-treating with a silane coupling agent after surface-treating with a silazane compound. The amount of the silazane compound used for the surface treatment is preferably 0.001% by mass to 0.3% by mass, more preferably 0.005% by mass to 0.2% by mass, relative to 100% by mass of the inorganic filler. is more preferable. Examples of the spherical fused silica surface-treated with hexamethyldisilazane include "SC2050" manufactured by Admatechs Co., Ltd. The amount of the silane coupling agent used for surface treatment is preferably 0.1% by mass to 6% by mass, and 0.2% by mass to 4% by mass with respect to 100% by mass of the inorganic filler. is more preferable, and 0.3% by mass to 3% by mass is even more preferable.

(E) The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis using a laser diffraction particle size distribution measuring apparatus, and the median diameter can be used as the average particle size for measurement. As the measurement sample, one obtained by ultrasonically dispersing an inorganic filler in water can be preferably used. LA-500, LA-750 manufactured by Horiba, Ltd., etc. can be used as the laser diffraction scattering type particle size distribution analyzer.

(E) In the case of blending an inorganic filler, the content is 100% by mass of non-volatile components in the photosensitive resin composition from the viewpoint of reducing the linear thermal expansion coefficient of the cured product and preventing distortion of the cured product. is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more from the viewpoint of improving heat resistance. . On the other hand, when the inorganic filler (E) is added, the content of the non-volatile component in the photosensitive resin composition is set to 100% by mass from the viewpoint of preventing deterioration of alkali developability and improving photocurability. In this case, the content is preferably 85% by mass or less, more preferably 75% by mass or less, and even more preferably 65% by mass or less.

<(F) Curing accelerator>
In the photosensitive resin composition of the present invention, the heat resistance, adhesiveness, chemical resistance, etc. of the cured product can be improved by further containing (F) a curing accelerator.
(F) The curing accelerator is not particularly limited, but includes, for example, amine-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, phosphonium-based curing accelerators, metal-based curing accelerators, and the like. These may be used singly or in combination of two or more.

Examples of the amine-based curing accelerator include, but are not limited to, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-tris(dimethylamino amine compounds such as methyl)phenol and 1,8-diazabicyclo(5.4.0)-undecene; These may be used singly or in combination of two or more.

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

Examples of imidazole-based curing accelerators include, but are not limited to, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-un Decylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate Tate, 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 isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 -hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc. Examples include imidazole compounds and adducts of imidazole compounds and epoxy resins. These may be used singly or in combination of two or more.

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

In the photosensitive resin composition of the present invention, as the curing accelerator (excluding metallic curing accelerators), it is preferable to use an amine-based curing accelerator or an imidazole-based curing accelerator. Among them, 4-dimethylaminopyridine, Particular preference is given to using 2-phenyl-4-methylimidazole. The content of the curing accelerator (excluding metallic curing accelerators) is preferably in the range of 0.005% by mass to 1% by mass when the non-volatile component in the photosensitive resin composition is 100% by mass. , more preferably in the range of 0.01 mass % to 0.08 mass %. If the amount is less than 0.005% by mass, the curing tends to be slow and a long curing time is required, and if the amount exceeds 1% by mass, the storage stability of the resin composition tends to decrease.

Metal-based curing accelerators are not particularly limited, but examples include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. organic zinc 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 organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used singly or in combination of two or more.

In the photosensitive resin composition of the present invention, it is preferable to use an organic cobalt complex as the metal-based curing accelerator, and it is particularly 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, preferably 30 ppm, based on the metal-based curing catalyst, when the total solid content of the photosensitive resin composition is 100% by mass. More preferably in the range of ~200 ppm.

<(G) Organic filler>
By further containing (G) an organic filler, the photosensitive resin composition of the present invention can relax the stress of the cured product and can prevent cracks from occurring when the cured product is obtained. (G) Organic fillers include, for example, rubber particles, polyamide fine particles, silicone particles, etc. In the present invention, rubber particles are preferably used.

As the rubber particles, any rubber particles may be used as long as they are microparticles of a resin that is insoluble and infusible in an organic solvent by chemically cross-linking a resin exhibiting rubber elasticity. For example, acrylonitrile-butadiene rubber particles. , butadiene rubber particles, and acrylic rubber particles. Specific examples of rubber particles include XER-91 (manufactured by Japan Synthetic Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, and IM101 (manufactured by Ganz Kasei Co., Ltd.). Examples include Paraloid EXL2655 and EXL2602 (manufactured by Kureha Chemical Industry Co., Ltd.), and AC3816N (manufactured by Ganz Kasei Co., Ltd.) is preferred.

The polyamide fine particles may be any fine particles of a resin having an amide bond and having a diameter of 50 μm or less. Examples thereof include aliphatic polyamides such as nylon, aromatic polyamides such as Kevlar, and polyamideimides. Specific examples of polyamide fine particles include VESTOSINT 2070 (manufactured by Daisel Huls KK) and SP500 (manufactured by Toray Industries, Inc.).

(G) The average particle size of the organic filler is preferably in the range of 0.005 μm to 1 μm, 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 can be determined, for example, by uniformly dispersing the organic filler in an appropriate organic solvent using ultrasonic waves or the like, and using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). can be used to create a particle size distribution of the organic filler on a mass basis, and the median diameter can be used as the average particle diameter for measurement.

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

<(H) Photosensitizer>
The photosensitive resin composition of the present invention contains (H) a photosensitizer as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine. Tertiary amines such as triethanolamine and the like may be added, and photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, thioxanthones and the like may be added. In the present invention, thioxanthones are preferably used as the photosensitizer, and 2,4-diethylthioxanthone is more preferably used. 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 organic solvents include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, and propylene glycol. Glycol ethers such as monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, and carbitol acetate, octane, decane, etc. Petroleum-based solvents such as aliphatic hydrocarbons, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, among which solvent naphtha and methyl ethyl ketone are preferred. These are used individually by 1 type or in combination of 2 or more types. When using an organic solvent, the content can be appropriately adjusted from the viewpoint of coating properties of the photosensitive resin composition.

<(J) Other additives>
(J) Other additives include, for example, fine particles such as melamine and organic bentonite, coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black and naphthalene black, and hydroquinone. , phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and other polymerization inhibitors, bentone, montmorillonite and other thickeners, silicone, fluorine and vinyl resin antifoaming agents, brominated epoxy compounds, acid-modified bromine Various additives such as epoxy compounds, antimony compounds, phosphorus compounds, flame retardants such as aromatic condensed phosphates and halogen-containing condensed phosphates, and thermosetting resins such as phenolic curing agents can be added. .

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

Applications of the photosensitive resin composition of the present invention are not particularly limited. It can be used in a wide range of applications requiring a resin composition, such as solder resist, underfill material, die bonding material, semiconductor encapsulating material, hole-filling resin, and 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 photosensitive resin A multilayer printed wiring board having a cured product of the composition as an interlayer insulating layer), and a resin composition for plating (a multilayer printed wiring board in which plating is formed on a cured product of a photosensitive resin composition). can be done.

<Photosensitive film>
The photosensitive resin composition of the present invention can be coated on a support substrate in a resin varnish state, and the organic solvent can be dried to form a resin composition layer to form a photosensitive film. Alternatively, a photosensitive film preliminarily formed on a support may be used by being laminated on the support substrate. The photosensitive film of the present invention can be laminated to various supporting substrates. Examples of the support substrate mainly include substrates such as glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates.

<Photosensitive film with support>
The photosensitive resin composition of the present invention can be suitably used in the form of a support-attached photosensitive film in which a resin composition layer is formed on a support. That is, the support-attached photosensitive film has a layer of a photosensitive resin composition formed on a support. Examples of the support include polyethylene terephthalate film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, triacetyl acetate film and the like, and polyethylene terephthalate film is particularly preferred.
Commercially available supports include, for example, Oji Paper Co., Ltd. product names "Alphan MA-410" and "E-200C", Shin-Etsu Film Co., Ltd. polypropylene films, and Teijin Limited product name "PS -25” and other PS series films and the like, but are not limited to these. These supports preferably have a release agent such as a silicone coating agent applied to the surface to facilitate removal of the resin composition layer. The thickness of the support is preferably in the range of 5 μm to 50 μm, more preferably in the range of 10 μm to 25 μm. When the thickness is less than 5 μm, the support (support film) tends to be easily torn when the support is peeled off before development. resolution tends to decrease. Also preferred are supports with low fisheyes. Here, the fish eye refers to foreign matter, undissolved matter, oxidative deterioration, etc. of the material being incorporated into the film when the film is produced by heat-melting the material, kneading, extruding, biaxial stretching, casting, etc. It is a thing.

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

By protecting the resin composition layer side of the support-attached photosensitive film with a protective film, it is possible to prevent dust from adhering to the surface of the resin composition layer and scratches on the surface of the resin composition layer. As the protective film, a film made of the same material as the 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, even more preferably in the range of 10 μm to 30 μm. If the thickness is less than 1 μm, the protective film tends to be difficult to handle, and if it exceeds 40 μm, the cost tends to be low. The protective film preferably has a lower adhesive strength between the resin composition layer and the protective film than the adhesive strength between the resin composition layer and the support.

The support-attached photosensitive film of the present invention can be produced by, for example, preparing a resin varnish by dissolving the photosensitive resin composition of the present invention in an organic solvent, and coating the resin varnish on the support, according to methods known to those skilled in the art. Then, the organic solvent is dried by heating or blowing hot air to form a resin composition layer. Specifically, first, after completely removing bubbles in the photosensitive resin composition by a vacuum defoaming method or the like, the photosensitive resin composition is applied onto a support, and the solvent is removed in a hot air oven or a far-infrared oven. A support-attached photosensitive film can be produced by removing, drying, and optionally 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. It can be dried in minutes to 13 minutes. The amount of the residual organic solvent in the resin composition layer is preferably 5% by mass or less, more preferably 2% by mass or less, relative to the total amount of the resin composition layer in order to prevent diffusion of the organic solvent in subsequent steps. is more preferable. A person skilled in the art can appropriately set suitable drying conditions by simple experiments. The thickness of the resin composition layer is preferably in the range of 5 μm to 500 μm, more preferably 10 μm to 200 μm, from the viewpoint of improving handleability and preventing deterioration of sensitivity and resolution inside the resin composition layer. more preferably in the range of 15 μm to 150 μm, still more preferably in the range of 20 μm to 100 μm, and most preferably in the range of 20 μm to 60 μm.

The coating method of the photosensitive resin composition includes, for example, gravure coating, micro gravure coating, reverse coating, kiss reverse coating, die coating, slot die, lip coating, comma coating, blade coating, A roll coating method, a knife coating method, a curtain coating method, a chamber gravure coating method, a slot orifice method, a spray coating method, a dip coating method, and the like can be mentioned.
The photosensitive resin composition may be applied in several times, may be applied in one time, or may be applied by combining a plurality of different methods. Among them, the die coating method is preferable because of its excellent uniform coatability. Also, in order to avoid contamination by foreign substances, it is preferable to perform the coating process in an environment such as a clean room where foreign substances are less likely to occur.

<Multilayer printed wiring board>
Next, an example of producing a multilayer printed wiring board using the photosensitive resin composition will be described.
When an interlayer insulating layer is produced using the photosensitive resin composition of the present invention, there are advantages such as (1) via opening can be performed all at once, and (2) via position accuracy is superior to laser opening. be done.

(Coating and drying process)
A photosensitive film is formed on the circuit board by applying the photosensitive resin composition in a resin varnish state directly onto the circuit board and drying the organic solvent. Examples of circuit boards include glass epoxy boards, metal boards, polyester boards, polyimide boards, BT resin boards, and thermosetting polyphenylene ether boards. Here, the term "circuit board" refers to a board having a patterned conductor layer (circuit) formed on one side or both sides of the board as described above. In addition, in a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, 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 here. included in the circuit board. The surface of the conductor layer may be roughened in advance by blackening treatment, copper etching, or the like.

As a coating method, screen printing is generally used for full surface printing, but any other coating method may be used as long as it 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 method. , brushing, or any other conventional application method can be used. After coating, drying is performed in a hot air oven, a far infrared oven, or the like, if necessary. The drying conditions are preferably 80° C. to 120° C. for 3 minutes to 13 minutes. Thus, a photosensitive film is formed on the circuit board.

(Lamination process)
When a photosensitive film with a support is used, the resin composition layer side is laminated on one side or both sides of a circuit board using a vacuum laminator. In the lamination step, when the photosensitive film with a support has a protective film, after removing the protective film, the photosensitive film and circuit board are preheated as necessary, and the resin composition layer is pressed. Then, while heating, it is crimped to the circuit board. In the photosensitive film of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum lamination method is preferably used.

The conditions of the lamination step are not particularly limited, but for example, the pressure bonding temperature (laminating temperature) is preferably 70° C. to 140° C., and the pressure bonding 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 pressure bonding time is preferably 5 seconds to 300 seconds, and the air pressure is 20 mmHg (26.7 hPa) or less. is preferred. Moreover, the lamination process may be of a batch type or a continuous type using rolls. A vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurized laminator manufactured by Meiki Seisakusho Co., Ltd., a roll type dry coater manufactured by Hitachi Industries, Ltd., and a Hitachi AIEC Co., Ltd. ) made vacuum laminator and the like. Thus, a photosensitive film is formed on the circuit board.

(Exposure process)
After the photosensitive film is provided on the circuit board by the coating and drying process or the lamination process, then, through the mask pattern, a predetermined portion of the resin composition layer is irradiated with actinic rays, and the irradiated portion of the resin composition layer is exposed. An exposure step for photocuring is performed. Actinic rays include, for example, ultraviolet rays, visible rays, electron beams, X-rays, and the like, and ultraviolet rays are particularly preferred. The irradiation dose of ultraviolet rays 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 brought into close contact with a printed wiring board and a non-contact exposure method in which a parallel light beam is used for exposure without close contact. Either method may be used. Further, when a support is present on the resin composition layer, exposure may be performed from above the support, or exposure may be performed after the support is peeled off.

(Development process)
After the exposure step, if there is a support on the resin composition layer, the support is removed, and then wet development or dry development is performed to remove the non-photocured portion (unexposed portion). A pattern can be formed by developing.

In the case of wet development, as the developer, a safe and stable developer having good operability such as an alkaline aqueous solution, an aqueous developer, and an organic solvent is used. is preferred. As a developing method, known methods such as spraying, rocking immersion, brushing, scraping, and the like are appropriately employed.

Organic solvents used as developers include, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol. It is monobutyl ether.

The concentration of such an organic solvent is preferably 2% by mass to 90% by mass with respect to the total amount of the developer. Moreover, the temperature of such an organic solvent can be adjusted according to the developability. Furthermore, such organic solvents can be used alone or in combination of two or more. Organic solvent-based developers used alone include, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone, propylene glycol 1-monomethyl ether 2 - Acetate (PGMEA), among which PGMEA is preferred in the present invention.

In the pattern formation of the present invention, two or more of the above-described developing methods may be used in combination, if desired. Development methods include a dip method, a battle method, a spray method, a high-pressure spray method, brushing, slapping, etc. The high-pressure spray method is suitable for improving resolution. When the spray method is employed, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

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

(plating process)
Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As dry plating, known methods such as vapor deposition, sputtering, and ion plating 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 the support in a vacuum vessel and heating and evaporating the metal. In the sputtering method, for example, the support is placed in a vacuum chamber, an inert gas such as argon is introduced, a DC voltage is applied, and the ionized inert gas collides with the target metal. A metal film can be formed on the insulating layer.

In the case of wet plating, uneven anchors are formed by subjecting the surface of the formed insulating layer to swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order. 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 minutes to 20 minutes. Examples of the swelling liquid include alkaline solutions such as sodium hydroxide solution and potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Security P and Swelling Dip Security SBU manufactured by Atotech Japan Co., Ltd. be able to. 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 obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, and the like. can. Also, the permanganate concentration in the alkaline permanganate solution is preferably 5% to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan Co., Ltd. The neutralization treatment with the neutralizing solution is performed by immersing the substrate in the neutralizing solution at 30° C. to 50° C. for 3 to 10 minutes. As the neutralizing liquid, an acidic aqueous solution is preferable, and as a commercial product, Reduction Solution Securigant P manufactured by Atotech Japan Co., Ltd. can be mentioned.

Next, electroless plating and electrolytic plating are combined to form a conductor layer. Alternatively, 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 for subsequent pattern formation, for example, a subtractive method, a semi-additive method, or the like 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. A semiconductor device can be manufactured by mounting a semiconductor chip on the conductive portion of the multilayer printed wiring board of the present invention. A "conducting part" is a "part for transmitting an electric signal in a multilayer printed wiring board", and the place may be a surface or an embedded part. Also, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting the semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively. Examples include a mounting method using a buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

INDUSTRIAL APPLICABILITY The photosensitive resin composition of the present invention can provide a resin composition having photosensitivity, excellent insulation reliability, and physical properties suitable for a buildup layer of a multilayer printed wiring board. Furthermore, it is possible to provide a cured product which is excellent in dielectric properties, water resistance and heat resistance and suitable for development with an organic solvent. These characteristics are described in detail below.

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 below. Specifically, the dielectric loss tangent can be measured by the cavity resonance perturbation method at a frequency of 5.8 GHz and a measurement temperature of 23°C. From the viewpoint of preventing heat generation at high frequencies and reducing signal delay and signal noise, the dielectric loss tangent is preferably 0.05 or less, more preferably 0.04 or less, and further preferably 0.03 or less. It is preferably 0.02 or less, even more preferably 0.013 or less. On the other hand, the lower limit of the dielectric loss tangent is not particularly limited, but may be 0.005 or more.

The water resistance (water absorption) of the cured product of the photosensitive resin composition of the present invention can be measured by the measurement method described in <Measurement of Water Resistance> below. The water absorption is preferably 3% or less, more preferably 2% or less, and 1% or less from the viewpoint of preventing voids from occurring during printed wiring board production and improving insulation reliability. More preferably, it is still more preferably 0.8% or less. On the other hand, the lower limit of water absorption is not particularly limited, but may be 0.01% or more, 0.1% or more, or 0.2% or more.

The heat resistance of the cured product of the photosensitive resin composition of the present invention can be measured by the measuring method described in <Evaluation of heat resistance> below. As an index of heat resistance, it is preferable to employ the glass transition point from the viewpoint of preventing deterioration of the cured product when a heat history is applied to the cured product. The glass transition point is preferably 110°C or higher. Although the upper limit of the glass transition point is not particularly limited, it is preferably 300° C. or less. Also, from the viewpoint of preventing distortion of the printed wiring board, a coefficient of thermal expansion may be employed as an index of heat resistance. The thermal expansion coefficient is preferably 10-30 ppm/°C.

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

<Adjustment of laminate for evaluation>
The copper layer of a glass epoxy substrate having a circuit formed of a copper layer of 18 mm thickness was roughened by CZ8100 (a surface treatment agent containing an organic acid, manufactured by MEC Co., Ltd.). Next, the resin composition layer of the support-attached photosensitive film obtained in Examples and Comparative Examples was brought into contact with the copper circuit surface, and laminated using a vacuum laminator (manufactured by Nichigo-Morton Co., Ltd., VP160). A laminate was prepared by laminating an epoxy substrate, the resin composition layer, and the support in this order. The crimping conditions were a crimping temperature of 80° C., a crimping pressure of 0.2 MPa, and a pressing time of 20 seconds after vacuuming for 20 seconds. The laminate is allowed to stand at room temperature for 1 hour or longer, and a pattern ^forming device is used to form round holes with a diameter of 80 mm using a round hole pattern on the support of the laminate. was exposed. After standing at room temperature for 30 minutes, the support was peeled off from the laminate. In the examples, the entire surface of the resin composition layer on the laminate was immersed in PGMEA (propylene glycol 1-monomethyl ether 2-acetate) at 30° C. as a developer for development, and then the developer was wiped off to obtain a density of 1 J/cm. ² , followed by heat treatment at 190° C. for 60 minutes to form an insulating layer having an opening with a diameter of 80 mm on the laminate. This was used as a laminate for evaluation.

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

<Adjustment of cured product for evaluation>
The resin composition layers of the support-attached photosensitive films obtained in Examples and Comparative Examples were exposed to ultraviolet light at 100 mJ/cm ² and photocured. After that, the entire surface of the resin composition layer was irradiated with ultraviolet rays at 1 J/cm ² and heat-treated at 190° C. for 90 minutes to form an insulating layer. After that, the support was peeled off to obtain a cured product for evaluation.

<Measurement method/evaluation method>
First, various measurement methods and evaluation methods will be explained.

<Evaluation of photosensitivity>
(Resolution)
As evaluation of resolution, the resist shape of the round hole of the laminate for evaluation was observed by SEM (magnification: 1000) and evaluated according to the following criteria.
◯: Good round hole shape, no curling or peeling.
x: The round hole shape spreads due to development, and there is curling and peeling.

(Developability)
As an evaluation of developability, the residue at the bottom of the round hole of the laminate for evaluation was observed by SEM (magnification: 1000), and the presence or absence of residue at the bottom of the round hole was evaluated according to the following criteria.
◯: There is no development residue on the substrate having a round hole with a diameter of 80 mm, and the development residue removability is excellent.
x: A development residue is present on the substrate having a round hole with a diameter of 80 mm, and the removability of the development residue is poor.

<Evaluation of insulation reliability>
An imide film having comb-shaped electrodes (line/space = 15 microns/15 microns) was placed so that the resin composition layer of the photosensitive film with a support obtained in Examples and Comparative Examples was in contact with the copper circuit surface. and laminated using a vacuum laminator (VP160, manufactured by Nichigo-Morton Co., Ltd.). The crimping conditions were a crimping temperature of 80° C., a crimping pressure of 0.2 MPa, and a pressing time of 20 seconds after vacuuming for 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. After that, it was irradiated with ultraviolet rays at 1 J/cm ² and further heat-treated at 190° C. for 60 minutes to obtain a laminate for evaluation. This laminate for evaluation was placed in a high-temperature and high-humidity chamber under an atmosphere of 130° C. and humidity of 85%, charged with a voltage of 3.3 V, and subjected to a HAST test in the chamber for 100 hours. After 100 hours, the insulation resistance value of the laminate for evaluation was evaluated according to the following criteria.
○: 10 ⁸ Ω or more ×: 10 ⁸ Ω or less

<Measurement of dielectric properties>
(Dielectric loss tangent)
An evaluation sample 1 was obtained by cutting the cured product for evaluation into a piece having a length of 80 mm and a width of 2 mm. The dielectric loss tangent of this evaluation sample 1 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>
(water absorption rate)
An evaluation sample 2 was obtained by cutting the cured product for evaluation into a 5 cm square. Subsequently, the mass of the evaluation sample 2 was measured, and the evaluation sample after the mass measurement was placed in boiling pure water and left for 1 hour in such a state that the evaluation sample 2 was completely submerged. After that, the evaluation sample 2 was taken out, the moisture on the surface was wiped off sufficiently, and the mass after water absorption was weighed to 0.1 mg, and the water resistance WA (%) was determined by the following formula. Four evaluation samples 2 were measured, and an average value was calculated.

WA = ((W1-W0)/W0) x 100
W0: Mass (g) of evaluation sample before water absorption
W1: Mass (g) of evaluation sample after water absorption

<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, and an evaluation sample 3 was obtained. Subsequently, using a thermomechanical analyzer TMA-SS6100 (manufactured by Seiko Instruments Inc.), thermomechanical analysis was performed by a tensile loading method. After the evaluation sample 3 was attached to the 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 (°C) was calculated from the point where the slope of the dimensional change signal in the second measurement changed. The thermal expansion coefficient was calculated as an average linear thermal expansion coefficient (ppm/°C) from 25°C to 150°C in the second measurement.

<Synthesis Example 1: Synthesis of an acrylate compound having a cresol novolak structure and an epoxy group>
To 700 g of diethylene glycol monoethyl ether acetate, 2050 g (equivalent weight: 10.0) of cresol novolac epoxy resin [manufactured by DIC Corporation, EPICLON N-660, epoxy equivalent weight: 205], 360 g of acrylic acid (equivalent weight: 5.0), and hydroquinone 1.5 g was charged, heated to 90° C. with stirring, and uniformly dissolved. Then, 5.9 g of triphenylphosphine was charged, the temperature was raised to 120° C., and the reaction was carried out for 12 hours. The obtained reaction liquid was diluted with a solvent to obtain an acrylate compound (manufactured product A).
・ Epoxy equivalent: 427
・ Acid value: 0.49mgKOH/g
・ Weight average molecular weight: 2000
・ Diethylene glycol monoethyl ether acetate solution with a solid content of 65% by mass

<Synthesis Example 2: Synthesis of a methacrylate compound having a bixylenol structure, a biscresol fluorene structure and an epoxy group>
In a reaction vessel, 190 g of a bixylenol-type epoxy resin (Mitsubishi Chemical Corporation YX4000, epoxy equivalent 185), 14 g of bisphenolacetophenone (phenolic hydroxyl equivalent 145), biscresol fluorene (JFE Chemical Co., Ltd., phenolic hydroxyl equivalent) 190) and 150 g of cyclohexanone were added and dissolved by stirring. Then, 0.5 g of a tetramethylammonium ammonium chloride solution was added dropwise, and the mixture was reacted at 180° C. for 5 hours under a nitrogen atmosphere. Next, the temperature is lowered to 60° C., and a mixture of 100 parts of isocyanatoethyl methacrylate (manufactured by Showa Denko K.K., trade name Karenz MOI, methacrylic equivalent 155) and 0.04 part of dibutyltin dilaurate is added dropwise through a dropping funnel. After completion, the reaction system was kept at 70° C. for 4 hours to eliminate the isocyanate group and obtain a methacrylate compound. After completion of the reaction, the mixture was filtered using a filter cloth and diluted with a solvent to obtain a methacrylate compound (product B).
・ Epoxy equivalent: 6400
・ Acid value: 0.73mgKOH/g
・ Weight average molecular weight: 29000
・ A 1:1 solution of MEK and cyclohexanone with a solids content of 25% by weight

<Examples 1 to 3, Comparative Example 1>
Each component was blended at the blending ratio shown in Table 1 and kneaded using a triple roll to prepare a resin varnish. Next, the resin varnish is uniformly coated on a 16 mm thick polyethylene terephthalate film (R310-16B, manufactured by Mitsubishi Plastics Co., Ltd., trade name) with a die coater and dried to form a resin composition layer with a 20 mm support. A photosensitive film was obtained. Drying was carried out using a hot air convection dryer at 75 to 120°C (average 100°C) for 4.5 minutes. Table 1 shows these measurement results and evaluation results.

The materials used are shown below.
(A) Component Epoxy resin HP-7200H (manufactured by DIC Corporation): dicyclopentadiene type epoxy resin, epoxy equivalent 280, solvent naphtha solution with 65% non-volatile content HP4032SS (manufactured by DIC Corporation): liquid naphthalene type Epoxy resin, epoxy equivalent weight 144
・ ZX1059 (manufactured by Nippon Steel Chemical Co., Ltd.): 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent 169
・YX4000HK (manufactured by Mitsubishi Chemical Corporation): crystalline bifunctional epoxy resin, epoxy equivalent 185
・ NC3000L (manufactured by Nippon Kayaku Co., Ltd.): biphenyl type epoxy resin, epoxy equivalent 269
(B) component active ester, cyanate ester, benzoxazine HPC8000-65T (manufactured by DIC Corporation): dicyclopentadiene type diphenol compound (polycyclopentadiene type diphenol compound) type active ester curing agent, solid content 65% toluene solution BA230S75 (manufactured by Lonza Japan Co., Ltd.): prepolymer of bisphenol A dicyanate, cyanate equivalent of about 232, non-volatile content of 75% by mass MEK solution PT30S (manufactured by Lonza Japan Co., Ltd.): phenol novolak type Polyfunctional cyanate ester resin cyanate equivalent of about 133, nonvolatile content of 85% by mass MEK solution Pd type benzoxazine (manufactured by Shikoku Kasei Co., Ltd.): benzoxazine monomer equivalent of 217, nonvolatile content of 60% by mass MEK solution (C ) Component (meth) acrylate-containing compound Product A Synthesized according to Synthesis Example 1 Product B Synthesized according to Synthesis Example 2 DPHA (manufactured by Nippon Kayaku Co., Ltd.): dipentaerythritol hexaacrylate, acid value 0.5 mg KOH / g
・ ZFR-1533H (manufactured by Nippon Kayaku Co., Ltd.): bisphenol F type epoxy acrylate, diethylene glycol monoethyl ether acetate solution with a solid content of 68%, modified with acid anhydride, acid value 70 mgKOH / g, weight average molecular weight: 14000
(D) Component Photopolymerization initiator IC819 (manufactured by BASF Japan Ltd.): Bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide OXE-01 (manufactured by BASF Japan Ltd.): 1, 2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)]
Component (E) Silica SOC2 (manufactured by Admatechs Co., Ltd.): spherical fused silica surface-treated with a phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573"), average particle size 0.5 mm
・ SOC1 (manufactured by Admatechs Co., Ltd.): spherical fused silica surface-treated with a phenylaminosilane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573", average particle size 0.24 mm)
(F) Component Curing accelerator DMAP (manufactured by Wako Pure Chemical Industries, Ltd.): 4-dimethylaminopyridine, MEK solution with a nonvolatile content of 2% by mass Co (III) (manufactured by Tokyo Kasei Co., Ltd.): Cobalt (III ) Acetylacetonate, MEK solution with a nonvolatile content of 1% by mass 2P4MZ (manufactured by Shikoku Kasei Co., Ltd.): 2-phenyl-4-methylimidazole, a DMF solution with a nonvolatile content of 5% by mass (G) Component rubber particles AC3816N ( Ganz Kasei Co., Ltd.): Core-shell type rubber particles (H) component Photosensitizer DETX-S (Nippon Kayaku Co., Ltd.): 2,4-diethylthioxanthone (I) component Solvent IP150 (solvent naphtha )
・MEK (methyl ethyl ketone)

From the results shown in Table 1, it can be seen that in the examples using the photosensitive resin composition of the present invention, it is possible to provide a photosensitive resin composition having excellent insulation reliability while having photosensitivity (resolution and developability). I found out. Furthermore, it has excellent dielectric properties and water resistance. On the other hand, in Comparative Example 1, although it has photosensitivity (resolution and developability), the component (B) is not blended and the acid anhydride-modified epoxy acrylate resin is used, so the insulation is poor. However, it is inferior in dielectric properties and water resistance, and cannot be used as a resin composition for interlayer insulation.

Claims (17)

(A) an epoxy resin,
(B) one or more curing agents selected from the group consisting of active ester curing agents and benzoxazine curing agents;
(C) a compound having a (meth)acrylate structure, and (E) an inorganic filler,
the active ester curing agent comprises phenol esters, the benzoxazine curing agent comprises Pd-type benzoxazine,
When the non-volatile component of the photosensitive resin composition is 100% by mass, the content of (E) the inorganic filler is 50% by mass or more,
A photosensitive resin composition for pattern formation including development after exposure of a resin composition layer, wherein the cured product of the photosensitive resin composition has a dielectric loss tangent of 0.005 to 0.05 . 2. The photosensitive resin composition according to claim 1, wherein the cured product of the photosensitive resin composition has a water absorption of 0.01 to 3%. (A) an epoxy resin,
(B) one or more curing agents selected from the group consisting of active ester curing agents and benzoxazine curing agents;
(C) a compound having a (meth)acrylate structure, and
(E) Inorganic filler
contains
the active ester curing agent comprises phenol esters, the benzoxazine curing agent comprises Pd-type benzoxazine,
When the non-volatile component of the photosensitive resin composition is 100% by mass, the content of (E) the inorganic filler is 50% by mass or more,
A photosensitive resin composition for pattern formation including development after exposure of a resin composition layer, wherein the water absorption of a cured product of the photosensitive resin composition is 0.01 to 3%. 4. The photosensitive resin composition according to any one of claims 1 to 3, wherein (A) an epoxy resin that is liquid at a temperature of 20°C and an epoxy resin that is solid at a temperature of 20°C are used in combination. The photosensitive resin composition according to any one of claims 1 to 4 , wherein the content of the component (A) is 3 to 50% by mass when the non-volatile component of the photosensitive resin composition is 100% by mass. The photosensitive resin composition according to any one of claims 1 to 5 , wherein the content of the component (B) is 1 to 30% by mass when the non-volatile component of the photosensitive resin composition is 100% by mass. 7. The photosensitive resin composition according to any one of claims 1 to 6 , wherein component (C) contains a polymer having a (meth)acrylate structure with a weight average molecular weight of 500 to 100,000. The photosensitive resin composition according to any one of claims 1 to 7 , wherein component (C) has an epoxy group. The photosensitive resin composition according to any one of claims 1 to 8 , wherein component (C) has an acid value of 20 mgKOH/g or less. The photosensitive resin composition according to any one of claims 1 to 9 , wherein the content of component (C) is 1 to 25% by mass when the non-volatile component of the photosensitive resin composition is 100% by mass. The photosensitive resin composition according to any one of claims 1 to 10 , further comprising (D) a photopolymerization initiator. The photosensitive resin composition according to any one of claims 1 to 11 , wherein the content of the inorganic filler (E) is 85% by mass or less when the non-volatile component of the photosensitive resin composition is 100% by mass. . The photosensitive resin composition according to any one of claims 1 to 11 , wherein the content of the inorganic filler (E) is 75% by mass or less when the non-volatile component of the photosensitive resin composition is 100% by mass. . 14. The photosensitive resin composition according to any one of claims 1 to 13 , which is used for an interlayer insulating layer of a multilayer printed wiring board. A photosensitive film with a support containing the photosensitive resin composition according to any one of claims 1 to 14. A multilayer printed wiring board comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 14. A semiconductor device comprising the multilayer printed wiring board according to claim 16 .