TW201901298A - Photosensitive resin composition - Google Patents

Abstract

An objective of the present invention is to provide a photosensitive resin composition with high resolution which provides excellent appearance, flexibility, and crack resistance to a film when molding the composition into a film shape, and is capable of obtaining a cured material with low has a low average linear expansion rate. The photosensitive resin composition contains: (A) a resin containing an ethylenically unsaturated group and a carboxyl group; (B) an inorganic filler having an average particle diameter of 0.5 [mu]m or more and 2.5 [mu]m or less, and a specific surface area of 1.4 m2/g or more and 10 m2/g or less; (C) a photopolymerization initiator; and (D) an epoxy resin. The content of the (B) component is 60 mass% or more and 85 mass% or less when the total solid content of the photosensitive resin composition is 100 mass%.

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition. Further, a photosensitive film obtained by using the photosensitive resin composition, a photosensitive film with a support, a printed wiring board, and a semiconductor device.

In a printed circuit board, as a permanent protective film for suppressing adhesion of solder to a portion where solder is not required and for suppressing corrosion of a circuit substrate, a solder resist may be provided. The solder resist is generally a photosensitive resin composition as described in Patent Document 1, for example. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-164304

[Problems to be solved by the invention]

A photosensitive resin composition for a solder resist is generally required to have resolution, insulation, solder heat resistance, gold plating resistance, moist heat resistance, crack resistance (TCT resistance), and for a fine wiring closet. HAST resistance of the ultra-accelerated high temperature and high humidity life test (HAST). In recent years, in view of the high density of printed circuit boards, solder resists have required further high performance. In particular, the demand for crack resistance has been increasing year by year, and it has become more and more important to have higher durability.

In order to improve crack resistance, for example, a method of filling an inorganic filler into a photosensitive resin composition is considered, but the adhesion to the covering is lowered, or the penetration of light is insufficient, so the sensitivity of the bottom of the via hole Deterioration, undercutting, or the possibility of insufficient opening due to vignette of light.

Further, from the viewpoint of productivity, the solder resist is required to be less likely to be broken during handling, and cracking or scattering of the resin is less likely to occur when the solder resist is cut.

An object of the present invention is to provide a cured resin composition which is excellent in crack resistance and has a low average coefficient of thermal expansion, and is excellent in appearance, flexibility, and resolution when formed into a film. A photosensitive film obtained by a photosensitive resin composition, a photosensitive film with a support, a printed circuit board, and a semiconductor device. [Means to solve the problem]

In order to solve the above problems, the inventors of the present invention have found that the photosensitive resin composition contains an inorganic filler having a predetermined average particle diameter and a predetermined specific surface area, and is excellent in resolution, crack resistance, and film formation. The appearance and softness of the film were improved, and the present invention was completed.

That is, the present invention includes the following. [1] A photosensitive resin composition containing a photosensitive resin composition of the following components: (A) a resin containing an ethylenically unsaturated group and a carboxyl group; and (B) an average particle diameter of 0.5 μm or more and 2.5 μm or less An inorganic filler having a specific surface area of 1.4 m ² /g or more and 10 m ² /g or less, (C) a photopolymerization initiator, and (D) an epoxy resin, and a solid component of the photosensitive resin composition When it is 100% by mass, the content of the component (B) is 60% by mass or more and 85% by mass or less. [2] The photosensitive resin composition according to [1], wherein the photosensitive resin composition is photocured, and the cured product which is thermally cured at 190 ° C for 90 minutes has an average linear thermal expansion coefficient of from 5 ° C to 150 ° C of 10 ppm or more. 45ppm or less. [3] The photosensitive resin composition according to [1] or [2] wherein the component (A) has a naphthalene skeleton. [4] The photosensitive resin composition according to any one of [1] to [3] wherein the component (A) is an epoxy (meth) acrylate containing an acid-modified naphthalene skeleton. [5] The photosensitive resin composition according to any one of [1] to [4] wherein the component (D) contains at least one of a biphenyl type epoxy resin and a tetraphenylethane type epoxy resin. . [6] of [1] to [5] of a photosensitive resin composition, wherein the specific surface area (B) component is 2m ² / g or more 7m ² / g or less. [7] The photosensitive resin composition according to any one of [1] to [6] wherein the component (B) contains cerium oxide. [8] A photosensitive film comprising the photosensitive resin composition according to any one of [1] to [7]. [9] A photosensitive film having a support, comprising: a support, and a photosensitive resin containing the photosensitive resin composition according to any one of [1] to [7], which is provided on the support Composition layer. [10] A printed circuit board comprising an insulating layer formed of a cured product of the photosensitive resin composition according to any one of [1] to [7]. [11] The printed circuit board of [10], wherein the insulating layer is a solder resist. [12] A semiconductor device comprising the printed circuit board of [10] or [11]. [Effects of the Invention]

According to the present invention, it is possible to provide a cured resin composition which is excellent in crack resistance and low in average linear thermal expansion coefficient, and which is excellent in appearance, flexibility, and resolution when formed into a film form; A photosensitive film obtained by a photosensitive resin composition, a photosensitive film with a support, a printed circuit board, and a semiconductor device.

Hereinafter, the photosensitive resin composition of the present invention, a photosensitive film, a photosensitive film with a support, a printed wiring board, and a semiconductor device will be described in detail.

[Photosensitive Resin Composition] The photosensitive resin composition of the present invention is a photosensitive resin composition containing (A) a resin containing an ethylenically unsaturated group and a carboxyl group, and (B) an average particle diameter of 0.5 μm. The above-mentioned 2.5 μm or less, the inorganic filler having a specific surface area of 1.4 m ² /g or more and 10 m ² /g or less, (C) a photopolymerization initiator, and (D) an epoxy resin, and a photosensitive resin composition When the total solid content is 100% by mass, the content of the component (B) is 60% by mass or more and 85% by mass or less.

When the photosensitive resin composition contains the components (A) to (D), a cured product having excellent crack resistance and a low average thermal expansion coefficient can be obtained, and the appearance and flexibility of the film when formed into a film shape can be obtained. And a photosensitive resin composition excellent in resolution. The photosensitive resin composition may further contain (E) a reactive diluent and (F) an organic solvent as necessary. Hereinafter, each component contained in the photosensitive resin composition will be described in detail.

<(A) Resin Containing Ethylene Unsaturated Group and Carboxyl Group> The photosensitive resin composition contains (A) a resin containing an ethylenically unsaturated group and a carboxyl group.

Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimine group, a nadic ylidene group, and a (meth) group. From the viewpoint of the reactivity of the acrylonitrile group and the photoradical polymerization, a (meth) acrylonitrile group is preferred. The "(meth)acryloyl group" means a methyl methacrylate group and an acryl fluorenyl group.

The component (A) has an ethylenically unsaturated group and a carboxyl group, and is not particularly limited as long as it is a compound capable of photoradical polymerization and can be subjected to alkali development, and has a carboxyl group and two or more ethylene in one molecule. A resin having an unsaturated group is preferred.

Examples of the resin containing an ethylenically unsaturated group and a carboxyl group include an acid-denatured unsaturated epoxy ester resin obtained by reacting an epoxy compound with an unsaturated carboxylic acid and further reacting an acid anhydride. Specifically, an acid-denatured unsaturated epoxy ester resin can be obtained by reacting an epoxy compound with an unsaturated carboxylic acid to obtain an unsaturated epoxy ester resin, and then reacting the unsaturated epoxy ester resin with an acid anhydride.

The epoxy compound can be used as long as it is a compound having an epoxy group in the molecule, and examples thereof include a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a hydrogenated bisphenol F type. An epoxy resin, a bisphenol S-type epoxy resin, a bisphenol epoxy resin obtained by reacting a bisphenol F-type epoxy resin with epichlorohydrin and denatured into a trifunctional or higher functional bisphenol F-type epoxy resin; Biphenol type epoxy resin such as phenol type epoxy resin or tetramethyl biphenol type; phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type novolac type epoxy resin, alkyl phenol novolac Phenolic epoxy resin such as epoxy resin; fluorine-containing epoxy resin such as bisphenol AF epoxy resin and perfluoroalkyl epoxy resin; naphthalene epoxy resin, dihydroxy naphthalene epoxy resin Polyhydroxynaphthalene type epoxy resin, naphthol type epoxy resin, binaphthol type epoxy resin, naphthyl ether type epoxy resin naphthol novolac type epoxy resin, by polyhydroxynaphthalene and aldehyde An epoxy resin having a naphthalene skeleton such as a naphthalene type epoxy resin obtained by a condensation reaction (containing a naphthalene skeleton) Oxygen resin); dixylenol type epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin; third butyl catechol type epoxy resin; Epoxy resin of condensed ring skeleton; glycidylamine type epoxy resin; glycidyl ester type epoxy resin; biphenyl type epoxy resin; linear aliphatic epoxy resin; epoxy having butadiene structure Resin; alicyclic epoxy resin; heterocyclic epoxy resin; epoxy resin containing spiro ring; cyclohexane dimethanol type epoxy resin; trimethylol type epoxy resin; tetraphenylethane type ring Oxygen oxime; polyglycidyl (meth) acrylate, glycidyl group-containing acrylic resin such as copolymer of glycidyl methacrylate and acrylate; fluorene type epoxy resin; halogenated epoxy resin.

From the viewpoint of lowering the average linear thermal expansion coefficient, an epoxy resin containing an aromatic skeleton is preferred. The aromatic skeleton herein also includes polycyclic aromatic and aromatic heterocyclic rings. In particular, an epoxy resin containing a naphthalene skeleton, an epoxy resin containing a condensed ring skeleton, a biphenyl type epoxy resin, a bisphenol F type epoxy resin, a bisphenol A type epoxy resin, a cresol novolac type epoxy A resin or a glycidyl ester type epoxy resin is preferred. In particular, since the rigidity of the molecule is increased, the movement of the molecule is suppressed, and as a result, the glass transition temperature of the cured product of the resin composition becomes high, and the average linear thermal expansion coefficient of the cured product is lowered, and naphthalene is contained. The epoxy resin of the skeleton, the epoxy resin having a fused ring skeleton, the biphenyl type epoxy resin is preferable, and the epoxy resin containing a naphthalene skeleton is more preferable. The epoxy resin containing a naphthalene skeleton is preferably a naphthalene type epoxy resin obtained by a condensation reaction of a polyhydroxynaphthalene type epoxy resin, a polyhydroxynaphthalene type epoxy resin, and a polyhydroxynaphthalene with an aldehyde.

Examples of the dihydroxynaphthalene type epoxy resin include 1,3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, and 1,6-dicondensed water. Glyceroxynaphthalene, 2,3-diglycidyloxynaphthalene, 2,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene, and the like.

The polyhydroxybinaphthalene type epoxy resin may, for example, be 1,1'-bis(2-glycidoxy)naphthyl or 1-(2,7-diglycidyloxy)-1'-(2'- Glycidyloxy)binaphthyl, 1,1'-bis(2,7-diglycidoxy)naphthyl and the like.

The naphthalene type epoxy resin obtained by the condensation reaction of polyhydroxynaphthalene with an aldehyde may, for example, be 1,1'-bis(2,7-diglycidyloxynaphthyl)methane or 1-(2,7). - diglycidyloxynaphthyl)-1'-(2'-glycidoxynaphthyl)methane, 1,1'-bis(2-glycidoxynaphthyl)methane.

Among these, a polyhydroxybiphthalene type epoxy resin having two or more naphthalene skeletons in one molecule, and a naphthalene type epoxy resin obtained by a condensation reaction of a polyhydroxynaphthalene with an aldehyde are preferable, especially one. 1,1'-bis(2,7-diglycidyloxynaphthyl)methane and 1-(2,7-diglycidyloxynaphthyl)-1'- having three or more epoxy groups in the molecule (2'-glycidyloxynaphthyl)methane, 1-(2,7-diglycidoxy)-1'-(2'-glycidoxy)binaphthyl, 1,1'-bis ( The 2,7-diglycidoxy)naphthyl group is suitable from the viewpoint of excellent average thermal expansion coefficient and heat resistance.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, cinnamic acid, and crotonic acid, and these may be used alone or in combination of two or more. In particular, acrylic acid or methacrylic acid is preferred from the viewpoint of improving the photocurability of the photosensitive resin composition. Further, in the present specification, an epoxy ester resin in which a reaction product of the above epoxy compound and (meth)acrylic acid is referred to as "epoxy (meth)acrylate" may be mentioned. Here, an epoxy compound is used. The epoxy group substantially disappears by reaction with (meth)acrylic acid. "(Meth)acrylate" means methacrylate and acrylate. There is a case where acrylic acid and methacrylic acid are collectively referred to as "(meth)acrylic acid".

Examples of the acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyrogallic anhydride, and diphenyl. The ketone tetracarboxylic dianhydride or the like may be used alone or in combination of two or more. In particular, succinic anhydride or tetrahydrophthalic anhydride is preferred from the viewpoint of improving the resolution of the cured product and improving the reliability of the insulation.

In the production of an acid-denatured unsaturated epoxy ester resin, an unsaturated carboxylic acid can be reacted with an epoxy resin in the presence of a catalyst to obtain an unsaturated epoxy ester resin, and then the unsaturated epoxy ester resin is reacted with an acid anhydride. . Further, a solvent or a polymerization inhibitor may be used as necessary.

The acid-denatured unsaturated epoxy ester resin is preferably an acid-denatured epoxy (meth) acrylate. The "epoxy" in the acid-denatured unsaturated epoxy ester resin means a structure derived from the above epoxy compound. For example, "acid-denatured bisphenol epoxy (meth) acrylate" means that the epoxy compound is a bisphenol type epoxy resin, and the unsaturated carboxylic acid is (meth)acrylic acid, and the obtained acid-denatured unsaturated epoxy is obtained. Ester resin. A suitable range of acid-denatured epoxy (meth) acrylates is a suitable range from epoxy compounds. That is, the acid-denatured unsaturated epoxy ester resin is an epoxy (meth) acrylate containing an acid-denatured naphthalene skeleton from the viewpoint of increasing the glass transition temperature of the cured product of the resin composition and lowering the average linear thermal expansion coefficient. It is better. The epoxy (meth) acrylate containing an acid-denatured naphthalene skeleton is obtained by reacting a reaction product of a naphthalene type epoxy resin and a (meth) acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. Compound.

A commercially available product can be used as the acid-denatured unsaturated epoxy ester resin. Specific examples thereof include "ZAR-2000" (a reaction product of a bisphenol A type epoxy resin, acrylic acid, and succinic anhydride) manufactured by Nippon Kayaku Co., Ltd. "ZFR-1491H", "ZFR-1533H" (reactive substance of bisphenol F type epoxy resin, acrylic acid, and tetrahydrophthalic anhydride), "PR-300CP" manufactured by Showa Denko Co., Ltd. (cresol novolac) Type epoxy resin, acrylic acid, and anhydride reactants). These may be used alone or in combination of two or more.

In another aspect of the resin containing an ethylenically unsaturated group and a carboxyl group, a (meth)acrylic resin which has a structural unit obtained by polymerizing (meth)acrylic acid is reacted with an epoxy compound containing an ethylenically unsaturated group, An unsaturated denaturing (meth)acrylic resin having an ethylenically unsaturated group is introduced. Examples of the epoxy compound containing an ethylenically unsaturated group include glycidyl methacrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and (meth)acrylic acid 3,4-epoxycyclohexyl. Ester and the like. Further, it is also possible to react a hydroxyl group generated when an unsaturated group is introduced with an acid anhydride. As the acid anhydride, the same article as the above acid anhydride can be used, and the suitable range is also the same.

A commercially available product can be used as the unsaturated modified (meth)acrylic resin. Specific examples include "SPC-1000" manufactured by Showa Denko Co., Ltd., "SPC-3000", and "CYCLOMER P (ACA) manufactured by Daicel Allnex Co., Ltd.). Z-250", "CYCLOMER P (ACA) Z-251", "CYCLOMER P (ACA) Z-254", "CYCLOMER P (ACA) Z-300", "CYCLOMER P (ACA) Z-320", etc.

The weight average molecular weight of the component (A) is preferably 1,000 or more, more preferably 1,500 or more, and more preferably 2,000 or more from the viewpoint of film formability. The upper limit is preferably 10,000 or less, more preferably 8,000 or less, and still more preferably 7,500 or less from the viewpoint of resolution. The weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

The acid value of the component (A) is preferably 0.1 mgKOH/g or more, more preferably 0.5 mgKOH/g or more, and 1 mgKOH/g or more, from the viewpoint of improving the alkali developability of the photosensitive resin composition. Better. On the other hand, from the viewpoint of suppressing the dissolution of the fine pattern of the cured product by the development and improving the reliability of the insulation, the acid value is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, and 100 mgKOH/g or less. good. The acid value herein refers to the residual acid value of the carboxyl group present in the component (A), and the acid value can be measured by the following method. First, after about 1 g of the resin solution to be tested, 30 g of acetone was added to the resin solution to uniformly dissolve the resin solution. Next, an appropriate amount of phenolphthalein as an indicator was added to the solution, and titration was carried out using a 0.1 N aqueous KOH solution. Next, the acid value is calculated by the following formula. Mathematical formula: A=10×Vf×56.1/(Wp×I)

Further, in the above formula, A represents an acid value (mgKOH/g), Vf represents a titer (mL) of KOH, Wp represents a mass (g) of the resin solution to be tested, and I represents a ratio of a nonvolatile component of the resin solution to be tested ( quality%).

In the case of producing the component (A), the ratio of the molar number of the epoxy group of the epoxy resin to the total number of carboxyl groups of the unsaturated carboxylic acid and the acid anhydride is from 1:1. A range of 0.8 to 1.3 is preferred, and a range of 1:0.9 to 1.2 is preferred.

When the solid content of the photosensitive resin composition is 100% by mass, the content of the component (A) is preferably 5% by mass or more, and is preferably 8 mass%. More than % is preferable, and more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, from the viewpoint of improvement in heat resistance.

<(B) Inorganic filler having an average particle diameter of 0.5 μm or more and 2.5 μm or less and a specific surface area of 1.4 m ² /g or more and 10 m ² /g or less> Photosensitive resin composition containing (B) an average particle diameter of 0.5 μm less than 2.5μm, specific surface area of 1.4m ² / g or more 10m ² / g or less of an inorganic filler. By containing the component (B), it is possible to provide a photosensitive resin composition capable of obtaining a cured product having a low average coefficient of thermal expansion.

The material of the inorganic filler is not particularly limited, and examples thereof include cerium oxide, aluminum oxide, glass, cordierite, cerium oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, and water aluminum. Mineral, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, barium carbonate, barium titanate, calcium titanate, magnesium titanate, titanium Barium oxide, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphotungstate, and the like. Among these, cerium oxide, aluminum oxide, and barium sulfate are suitable, and cerium oxide is particularly suitable. Further, cerium oxide is preferably spherical cerium oxide. The inorganic fillers may be used singly or in combination of two or more.

The average particle diameter of the inorganic filler is 0.5 μm or more, preferably 0.6 μm or more, and preferably 0.7 μm or more from the viewpoint of obtaining a cured product having a low average coefficient of thermal expansion. The upper limit of the average particle diameter is 2.5 μm or less, preferably 2 μm or less, and preferably 1.8 μm or less from the viewpoint of obtaining excellent resolution. For example, "ADMAFINE" manufactured by Admatechs Co., Ltd., "SFP series" manufactured by Electrochemical Industries Co., Ltd., and "SP(H) manufactured by Nippon Steel & Metals Material Co., Ltd." "Sciqas series" manufactured by Nippon Chemical Co., Ltd., "SEAHOSTAR series" manufactured by Nippon Shokubai Co., Ltd., and "AZ series" and "AX" manufactured by Nippon Steel & Metals Material Co., Ltd. "B series" and "BF series" manufactured by 堺Chemical Industries Co., Ltd., and the like.

The average particle diameter of the inorganic filler can be measured by a laser diffraction scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction scattering type particle size distribution measuring apparatus, and the particle diameter of the cumulative frequency of 50% (d50) can be determined as an average particle diameter. . The sample to be tested is preferably a sample obtained by dispersing an inorganic filler in water by ultrasonic waves. For the laser diffraction scattering type particle size distribution measuring apparatus, "LA-500" manufactured by Horiba, Ltd., and "SALD-2200" manufactured by Shimadzu Corporation can be used.

The particle diameter (D ₉₀ ) when the cumulative frequency of the inorganic filler is 90% is preferably 0.5 μm or more, preferably 0.8 μm or more, and more preferably 1 μm from the viewpoint of obtaining a cured product having a low average coefficient of thermal expansion. the above. The upper limit of D ₉₀ is 5.5 μm or less, preferably 5 μm or less, and preferably 4.5 μm or less from the viewpoint of obtaining excellent resolution. D ₉₀ can be measured by the same method as the average particle diameter.

The inorganic filler can be classified by a classifier or the like to obtain an inorganic filler having a desired average particle diameter.

The specific surface area of the inorganic filler is 1.4 m ² /g or more, preferably 1.7 m ² /g or more, and preferably 2 m ² /g or more, from the viewpoint of obtaining excellent resolution. The upper limit of the specific surface area, obtained from the cracking resistance is excellent in point of view of 10m ² / g or less, and is suitably 9m ² / g or less, preferably 8m ² / g or less, more preferably 7m ² / g Hereinafter, it is 5 m ² /g or less.

The specific surface area of the inorganic filler can be measured by the method described later (preparation of the inorganic filler).

The inorganic filler is an amine-based decane coupling agent, an epoxy decane coupling agent, a mercapto decane coupling agent, a decane coupling agent, an alkoxy decane compound, or the like, from the viewpoint of improving moisture resistance and dispersibility. It is preferred to treat one or more surface treatment agents such as an organic decazane compound or a titanate coupling agent. For example, "KBM403" (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-Mercaptopropylamine) manufactured by Shin-Etsu Chemical Co., Ltd., may be used as a commercial product of the surface treatment agent. "KBE903" (3-aminopropyltriethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethyl) manufactured by Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldioxane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type decane coupling agent).

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and 0.2 mg/m ² or more from the viewpoint of improving the dispersibility of the inorganic filler. Better. On the other hand, from the viewpoint of suppressing the melt viscosity of the resin varnish or the melt viscosity of the sheet form, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and more preferably 0.5 mg/m ² or less. good.

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed by a solvent such as methyl ethyl ketone (MEK). Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonically washed at 25 ° C for 5 minutes. The supernatant was removed to dry the solid component, and then the amount of carbon per unit surface area of the inorganic filler was measured using a carbon analyzer. For the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

The content of the inorganic filler is 60% by mass or more, preferably 61%, when the non-volatile component in the photosensitive resin composition is 100% by mass, from the viewpoint of obtaining a cured product having a low average thermal expansion coefficient. More than %, preferably more than 62% by mass. The upper limit is 85% by mass or less, preferably 80% by mass or less, and preferably 70% by mass or less from the viewpoint of suppressing light reflection.

<(C) Photopolymerization Initiator> The photosensitive resin composition contains (C) a photopolymerization initiator. By containing the component (C), the photosensitive resin composition can be photocured efficiently.

The component (C) is not particularly limited, and examples thereof include 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone and 2-(dimethylamino). -2-[(4-methylphenyl)methyl]-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio) α-Aminoalkylphenone photopolymerization initiator such as phenyl]-2-morpholinylpropan-1-one; 1-[9-ethyl-6-(2-methylbenzylidene) An oxime ester photopolymerization initiator such as -9H-carbazol-3-yl]-ethanone-1-(O-acetamidofluorene); benzophenone, methylbenzophenone, orthophthalic acid Kean acid, benzhydryl ethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzene Mercapto)phosphine oxide, ethyl-(2,4,6-trimethylbenzylidene)phenylphosphonate, 4,4'-bis(diethylamino)benzophenone, 1 -hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl] 2-hydroxy-2-methyl-l-propan-1-one, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, etc., in addition to sulfonium salt photopolymerization Starter and the like. Either of them may be used alone or in combination of two or more.

Further, in the photosensitive resin composition, in combination with the component (C), as a photopolymerization initiation aid, it may contain N,N-dimethylamino benzoic acid ethyl ester, N,N-dimethylamino benzoic acid different a tertiary amine such as amyl ester, amyl 4-dimethylaminobenzoate, triethylamine or triethanolamine, and may also contain, for example, pyrazolines, anthraquinones, coumarins, xanthones, and thiophenes. Light sensitizers such as tons of ketones. Either of them may be used alone or in combination of two or more.

Specific examples of the component (C) include "Omnirad 907", "Omnirad 369", "Omnirad 379", "Omnirad 819", "Omnirad TPO" manufactured by IGM, "Irgacure OXE-01" manufactured by BASF Corporation, and "Irgacure OXE-02". "Irgacure 819", "N-1919" made by ADEKA Corporation.

The content of the component (C) is preferably 0.01% by mass or more, when the total amount of the solid content of the photosensitive resin composition is 100% by mass, from the viewpoint of sufficiently curing the photosensitive resin composition and improving the reliability of the insulation. It is preferably 0.03 mass% or more, more preferably 0.05 mass% or more. On the other hand, the upper limit is preferably 1% by mass or less, preferably 0.5% by mass or less, and more preferably 0.3% by mass or less from the viewpoint of suppressing the deterioration of the resolution.

<(D) Epoxy Resin> The photosensitive resin composition contains (D) an epoxy resin. By containing the (D) component, the insulation reliability can be improved. However, the component (D) referred to herein does not include an epoxy resin containing an ethylenically unsaturated group and a carboxyl group.

Examples of the component (D) include a fluorine-containing epoxy resin such as a bisphenol AF epoxy resin and a perfluoroalkyl epoxy resin; a bisphenol A epoxy resin; and a bisphenol F epoxy resin; Bisphenol S type epoxy resin; dixylenol type epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin; naphthol novolac type epoxy resin; phenol novolac type epoxy resin; Tributyl-catechol type epoxy resin: naphthalene type epoxy resin; naphthol type epoxy resin; fluorene type epoxy resin; glycidyl amine type epoxy resin; glycidyl ester type epoxy resin; Phenolic novolac type epoxy resin; biphenyl type epoxy resin; linear aliphatic epoxy resin; epoxy resin having butadiene structure; alicyclic epoxy resin; alicyclic epoxy resin having ester skeleton Heterocyclic epoxy resin; epoxy resin containing spiro ring; cyclohexane dimethanol type epoxy resin; naphthyl ether type epoxy resin; trimethylol type epoxy resin; tetraphenylethane type Epoxy resin, halogenated epoxy resin, etc., from the viewpoint of improving adhesion, bisphenol F type epoxy resin, biphenyl type epoxy tree The fat is preferred, and the biphenyl type epoxy resin is preferred. In addition, from the viewpoint of improving heat resistance, a naphthalene type epoxy resin, a naphthol type epoxy resin, a fluorene type epoxy resin, a naphthyl ether type epoxy resin, and a tetraphenylethane type epoxy resin are used. Preferably, a tetraphenylethane type epoxy resin is preferred. The epoxy resins may be used alone or in combination of two or more. The component (D) is preferably at least one selected from the group consisting of a biphenyl type epoxy resin and a tetraphenylethane type epoxy resin from the viewpoint of improving adhesion and heat resistance.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, it is preferred that at least 50% by mass or more of the epoxy resin having two or more epoxy groups in one molecule is used. Two or more epoxy resins may be used in combination with the component (E).

Specific examples of the epoxy resin include "HP4032", "HP4032D", "HP4032SS", "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation, "828US" manufactured by Mitsubishi Chemical Corporation, and "jER828EL" (double Phenol A type epoxy resin), "JER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin) "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and "YD-8125G" (bisphenol A) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. "Epoxy resin", "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., Ltd., "CELLOXIDE 2021P" manufactured by Daicel Co., Ltd. (alicyclic epoxy resin having an ester skeleton), "PB -3600" (epoxy resin with butadiene structure), "ZX1658" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., "ZX1658GS" (liquid 1,4-glycidylcyclohexane), manufactured by Mitsubishi Chemical Corporation "630LSD" (glycidylamine type epoxy resin), "E-7432" and "E-7632" manufactured by Daikin Industries Co., Ltd. (perfluoroalkyl type) Epoxy resin), "HP-4700", "HP-4710" (naphthalene type 4-functional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" manufactured by DIC Corporation (cresol novolac type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311- G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (stretching naphthyl ether epoxy resin), "EPPN-502H" manufactured by Nippon Kayaku Co., Ltd. (trisphenol epoxy) "Resin", "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), "YSLV-80XY" (tetramethyl bisphenol F type epoxy resin), "YX4000H" manufactured by Mitsubishi Chemical Corporation, "YL6121" (biphenyl type epoxy resin), "YX4000HK" (dixylenol type epoxy resin), "YX8800" (蒽 type epoxy resin), "PG-100" manufactured by Osaka Gas Chemical Co., Ltd., "CG-500", "YL7800" by Mitsubishi Chemical Corporation (芴-type epoxy resin), "1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "1031S" (tetraphenylethane type epoxy resin), "YL7760" (bisphenol AF) Type epoxy resin).

The content of the component (D) is preferably 1 when the solid content of the photosensitive resin composition is 100% by mass from the viewpoint of obtaining an insulating layer which exhibits excellent tensile strength and insulation reliability. The mass% or more is preferably 5% by mass or more, and more preferably 8% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention can be exerted, and is preferably 25% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less.

The epoxy equivalent of the epoxy resin is preferably from 50 to 5,000, preferably from 50 to 3,000, more preferably from 80 to 2,000, still more preferably from 110 to 1,000. By setting it within this range, the cured product of the photosensitive resin composition has a sufficient crosslinking density, and an insulating layer having a small surface roughness can be produced. Further, the epoxy equivalent can be measured in accordance with JIS K7236 and is a mass of a resin containing 1 equivalent of an epoxy group.

The weight average molecular weight of the epoxy resin is preferably from 100 to 5,000, preferably from 250 to 3,000, more preferably from 400 to 1,500. Here, the weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

<(E) Reactive diluent> The photosensitive resin composition may further contain (E) a reactive diluent. By containing the (E) component, the photoreactivity can be improved. As the component (E), for example, a photosensitive (meth) acrylate compound having one or more (meth) acrylonitrile groups in one molecule and being liquid, solid or semi-solid at room temperature can be used. Room temperature means about 25 ° C. The "(meth)acryloyl group" means an acryloyl group and a methacryloyl group.

Typical photosensitive (meth) acrylate compounds include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate, ethylene glycol, methoxytetraethylene glycol, and poly Mono- or diacrylates of diols such as ethylene glycol and propylene glycol, acrylamides such as N,N-dimethyl decylamine and N-methylol acrylamide, and N,N-dimethyl Aminoalkyl acrylate such as amine ethyl acrylate, polyhydric alcohol such as trimethylolpropane, pentaerythritol or dipentaerythritol or addition of such ethylene oxide, propylene oxide or ε-caprolactone a phenol such as a polyvalent acrylate, a phenoxy acrylate or a phenoxyethyl acrylate, or an acrylate such as an ethylene oxide or a propylene oxide adduct, or a trimethylolpropane A glycidyl ether-derived epoxy acrylate such as triglycidyl ether, a melamine acrylate, and/or a methacrylate corresponding to the above acrylate. Among these, a polyvalent acrylate or a polyvalent methacrylate is preferable, and for example, a trivalent acrylate or a methacrylate, trimethylolpropane tri(meth)acrylate, Pentaerythritol tri(meth)acrylate, trimethylolpropane EO addition tris(meth)acrylate, glycerin PO addition tris(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetrafuranmethyl Alcohol oligomeric (meth) acrylate, ethyl carbitol oligo (meth) acrylate, 1,4-butanediol oligo (meth) acrylate, 1,6-hexanediol oligomerization ( Methyl) acrylate, trimethylolpropane oligomeric (meth) acrylate, pentaerythritol oligomeric (meth) acrylate, tetramethylol methane tetra(meth) acrylate, dipentaerythritol hexa(methyl) Acrylate, N, N, N', N'-fluorene (β-hydroxyethyl) ethyl diamine (meth) acrylate, etc., trivalent or higher acrylate or methacrylate, Tris(2-(methyl)propenyloxyethyl)phosphate, tris(2-(methyl)propenyloxypropyl)phosphate, tris(3-(methyl)propenyloxypropyl Phosphate ester, tris(3-(methyl) propylene Benzyl-2-hydroxyoxypropyl)phosphate, bis(3-(methyl)propenyl-2-hydroxyoxypropyl)(2-(methyl)propenyloxyethyl)phosphate, A phosphotriester (meth) acrylate such as (3-(meth)acrylinyl-2-hydroxyoxypropyl)bis(2-(methyl)propenyloxyethyl)phosphate. Any of these photosensitive (meth) acrylate compounds may be used singly or in combination of two or more.

In the case of blending the component (E), the content of the photosensitive resin composition is 100% by mass, and the content of the photosensitive resin composition is 100% by mass. It is preferably 0.5% by mass to 10% by mass, and preferably 2% by mass to 8% by mass.

<(F) Organic Solvent> The photosensitive resin composition may further contain (G) an organic solvent. The varnish viscosity can be adjusted by containing the (G) component. (G) The organic solvent may, for example, be a ketone such as ethyl methyl ketone or cyclohexanone; an aromatic hydrocarbon such as toluene, xylene or tetramethylbenzene; methyl cellosolve; butyl cellosolve; Glycol ethers such as carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, butyl cellosolve An ester such as acetate, carbitol acetate or ethyl diglycol acetate, an aliphatic hydrocarbon such as octane or decane, or petroleum solvent such as petroleum ether, petroleum brain, hydrogenated petroleum brain or solvent oil. Wait. These may be used alone or in combination of two or more. In the case of using an organic solvent, the content thereof can be appropriately adjusted from the viewpoint of coatability of the photosensitive resin composition.

<(G) Other Additives> The photosensitive resin composition may further contain (G) other additives to the extent that the object of the present invention is not inhibited. (G) other additives, for example, fine particles such as thermoplastic resin, organic filler, melamine, organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene may be added. Coloring agent such as black, hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, gallic phenol, etc., polymerization inhibitor, bentonite, montmorillonite, etc. Flame retardant, fluorine-based, vinyl resin-based antifoaming agent, brominated epoxy compound, acid-denatured brominated epoxy compound, hydrazine compound, phosphorus-based compound, aromatic condensed phosphate, halogen-containing condensed phosphate Various additives such as a thermosetting resin such as a phenolic curing agent or a cyanate curing agent.

The photosensitive resin composition can be suitably mixed by mixing the above-mentioned components (A) to (D) as an essential component, and the above-mentioned components (E) to (G) as an optional component are appropriately mixed, and it is necessary to use three rolls as necessary. A resin varnish is produced by kneading or stirring a mixing means such as a machine, a ball mill, a bead mill, a sand mixer, or a stirring means such as a super mixer or a planetary mixer.

<Physical properties and use of the photosensitive resin composition> The cured product of the photosensitive resin composition of the present invention is photocured and then cured at 190 ° C for 90 minutes, and exhibits a low average thermal expansion coefficient. That is, an insulating layer and a solder resist having a low average thermal expansion coefficient are produced. The average linear thermal expansion coefficient is preferably 45 ppm or less, preferably 44 ppm or less, more preferably 43 ppm or less, and 42 ppm or less. The lower limit is not particularly limited and may be set to 10 ppm or more. The measurement of the average linear thermal expansion coefficient can be carried out according to the method described in <Measurement of the average linear expansion ratio> described later.

Since the photosensitive resin composition of the present invention contains the component (B) having an average particle diameter and a specific surface area within a predetermined range, even if the content of the component (B) is large, the composition exhibits excellent resolution. Therefore, the minimum pore diameter without residue is preferably 100 μm or less, preferably 90 μm or less, more preferably 80 μm or less and 70 μm or less. The lower limit is not particularly limited and may be 0.1 μm or more. Further, from the viewpoint of excellent resolution, usually, there is no resin filling or peeling between L/S (line width/pitch). The lower limit is not particularly limited, and may be set to 1 μm / 1 μm or more. The evaluation of the resolution can be evaluated in accordance with the method described in "Evaluation of resolution and crack resistance" described later.

After the photosensitive resin composition of the present invention is photocured, the cured product which is thermally cured at 190 ° C for 90 minutes exhibits excellent properties against cracking. That is, an insulating layer and a solder resist excellent in crack resistance are produced. The temperature rise test between -65 ° C and 150 ° C usually does not observe cracking and peeling even if it is repeated 500 times. The evaluation of the crack resistance can be evaluated according to the method described in the "Evaluation of resolution and crack resistance" described later.

The use of the photosensitive resin composition of the present invention is not particularly limited, and can be widely used for a photosensitive film, a photosensitive film with a support, an insulating resin sheet such as a prepreg, and a circuit board (for laminate use, multilayer printing). For circuit board applications, etc., solder resists, underfill materials, grain bonding materials, semiconductor sealing materials, hole-filling resins, and component embedding resins, etc., it is necessary to use a photosensitive resin composition. In particular, a photosensitive resin composition for an insulating layer of a printed circuit board (a printed circuit board having a cured product of a photosensitive resin composition as an insulating layer) and a photosensitive resin composition for an interlayer insulating layer (for a photosensitive resin) Photosensitive resin composition (a printed circuit board as an interlayer insulating layer), a photosensitive resin composition for plating (a printed circuit board formed by plating on a cured product of a photosensitive resin composition), and photosensitivity for a solder resist Resin composition (a printed circuit board using a cured product of a photosensitive resin composition as a solder resist).

[Photosensitive Film] The photosensitive resin composition of the present invention is applied onto a support substrate in a state of a resin varnish, and the organic solvent is dried to form a photosensitive resin composition layer, whereby a photosensitive film can be obtained. Further, a photosensitive film formed in advance on the support may be laminated on a support substrate and used. The photosensitive film can be laminated on various support substrates. The support substrate is mainly a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting polyphenylene ether substrate.

[Photosensitive film with a support] The photosensitive resin composition of the present invention is suitably used in the form of a photosensitive film having a support on which a photosensitive resin composition layer is formed on a support. In other words, the photosensitive film with a support includes a support and a photosensitive resin composition layer formed on the support and formed of the photosensitive resin composition of the present invention.

The support may, for example, be a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a polyvinyl alcohol film, a triethyl decyl acetate film, or the like, especially A polyethylene terephthalate film is preferred.

For example, a product such as "ALPHAN MA-410" manufactured by Oji Paper Co., Ltd., "E-200C", a polypropylene film manufactured by Shin-Etsu Film Co., Ltd., and a product name "PS-25" manufactured by Teijin Co., Ltd. A polyethylene terephthalate film or the like such as a PS series is not limited thereto. In order to facilitate removal of the photosensitive resin composition layer, these supports may be applied to a surface of a release agent such as a polyoxymethylene coating agent. The thickness of the support is preferably in the range of 5 μm to 50 μm, and preferably in the range of 10 μm to 25 μm. By setting the thickness to 5 μm or more, the support is prevented from being cracked when the support is peeled off before development, and by setting the thickness to 50 μm or less, the resolution at the time of exposure on the support can be improved. In addition, a support having a small fisheye phenomenon is preferred. Here, the fisheye phenomenon means that when a film is produced by heat fusion, kneading, extrusion, biaxial stretching, casting, or the like, foreign matter, undissolved matter, oxidative degradation material, or the like of the material is absorbed into the film. phenomenon.

Further, in order to reduce light scattering during exposure by active energy rays such as ultraviolet rays, the support is preferably excellent in transparency. The support, specifically, the haze (the haze normalized by JIS K6714) as the transparency index is preferably 0.1 to 5. Further, the photosensitive resin composition layer can be protected by a protective film.

By protecting the photosensitive resin composition layer side of the photosensitive film with a support by a protective film, it is possible to prevent dust or the like from adhering or damaging the surface of the photosensitive resin composition layer. As the protective film, a film composed of the same material as the above support can be used. The thickness of the protective film is not particularly limited, and is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and still more preferably in the range of 10 μm to 30 μm. When the thickness is set to 1 μm or more, the usability of the protective film can be improved, and if it is 40 μm or less, the inexpensiveness tends to be improved. Further, in the protective film, it is preferable that the adhesion force of the photosensitive resin composition layer and the protective film is small with respect to the adhesion force of the photosensitive resin composition layer and the support.

The photosensitive film of the support of the present invention can be prepared by dissolving the photosensitive resin composition of the present invention in an organic solvent to prepare a resin varnish, applying the resin varnish to the support, and blowing it by heating or hot air. The organic solvent is dried to form a photosensitive resin composition layer to be produced. Specifically, the photosensitive resin composition can be applied to the support by first removing the bubbles in the photosensitive resin composition by a vacuum defoaming method or the like, and the solvent can be applied by a hot air oven or a far infrared furnace. After removing and drying, it is necessary to laminate a protective film on the obtained photosensitive resin composition layer, and the photosensitive film with a support is manufactured. The specific drying conditions vary depending on the curability of the photosensitive resin composition or the amount of the organic solvent in the resin varnish, and the resin varnish containing 30% by mass to 60% by mass of the organic solvent may be in the range of 80 ° C to 120 ° Dry at °C for 3 minutes to 13 minutes. The amount of the organic solvent remaining in the photosensitive resin composition layer is preferably 5% by mass or less based on the total amount of the photosensitive resin composition layer from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step. It is preferably 2% by mass or less. The industry can appropriately set suitable drying conditions by simple experimentation. The thickness of the photosensitive resin composition layer is preferably from 5 μm to 500 μm, and is preferably from 10 μm to 200 μm, from the viewpoint of improving the usability and suppressing the sensitivity and resolution in the photosensitive resin composition layer. The range is preferably in the range of 15 μm to 150 μm, more preferably in the range of 20 μm to 100 μm, and particularly preferably in the range of 20 μm to 60 μm.

Examples of the coating method of the photosensitive resin composition include a gravure coating method, a micro gravure coating method, a reverse coating method, an anastomosis reversal coating method, a die coating method, a slit die method, and a lip coating method. , lack of angle coating method, blade coating method, roll coating method, blade coating method, curtain coating method, chamber gravure coating method, slit die hole method, spray coating Method, dip coating method, and the like. The photosensitive resin composition may be applied in several times or in one pass, and may be applied in combination in a plurality of different manners. In particular, a mold application method having excellent uniform coating properties is preferred. In addition, in order to avoid foreign matter incorporation or the like, it is preferable to carry out the coating step in an environment where the generation of foreign matter such as a clean room is small.

The photosensitive resin composition layer of the photosensitive film of the support of the present invention exhibits excellent properties of flexibility. Even if the photosensitive resin composition layer was cut with a utility knife, scattering or cracking of the photosensitive resin composition was not observed, and even if the photosensitive resin composition layer was bent by 180°, no observation was observed. It is preferable that the photosensitive resin composition is scattered or cracked. The flexibility can be measured in accordance with the description of the "evaluation of the appearance and flexibility of the film" described later.

[Printed Circuit Board] The printed wiring board of the present invention contains an insulating layer formed of a cured product of the photosensitive resin composition of the present invention. The insulating layer is preferably used as a solder resist.

Specifically, the printed wiring board of the present invention can be produced by using the above-mentioned photosensitive film or a photosensitive film with a support. The following description will be made on the case where the insulating layer is a solder resist.

<Coating and Drying Step> The photosensitive resin composition is directly applied onto a circuit board in a resin varnish state, 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. Here, the circuit substrate herein refers to a substrate in which a patterned conductor layer (circuit) is formed on one surface or both surfaces of the substrate as described above. In addition, in a multilayer printed circuit board in which a conductor layer and an insulating layer are alternately laminated, a substrate on one or both sides of the outermost layer of the multilayer printed circuit board is a patterned conductor layer (circuit), which is also included herein. The so-called circuit board. Further, the surface of the conductor layer may be roughened in advance by blackening treatment, copper etching, or the like.

The coating method is generally a total printing using a screen printing method. In other respects, any means can be used as long as it is a coating method which can be uniformly applied. For example, spray coating method, hot melt coating method, bar coating method, applicator method, blade coating method, blade coating method, air knife coating method, curtain coating method, roll coating method, gravure coating A cloth method, an offset printing method, a dip coating method, a brush coating method, and other usual coating methods can be used. After coating, it is necessary to dry in a hot air furnace or a far infrared furnace as necessary. The drying conditions are preferably carried out at 80 ° C to 120 ° C for 3 minutes to 13 minutes. In this manner, a photosensitive film can be formed on the circuit substrate.

<Laminating Step> In the case of using a photosensitive film with a support, the photosensitive resin composition layer side is laminated on one side or both sides of the circuit board using a vacuum laminator. In the case where the photosensitive film with a support has a protective film in the lamination step, after removing the protective film, the photosensitive film and the circuit board with the support are required to be preheated, and the photosensitive resin composition is used. The layer is pressurized and heated while being pressed against the circuit substrate. A photosensitive film with a support is preferably a method of laminating a circuit board under reduced pressure by vacuum lamination.

The conditions of the laminating step are not particularly limited, for example, the pressing temperature (lamination temperature) is set to 70 ° C to 140 ° C, and the pressing pressure is set to 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 set to 5 seconds to 300 seconds, and it is preferred to carry out lamination under reduced pressure of 20 mmHg (26.7 hPa) or less. Alternatively, the laminating step can be batch or continuous using a drum. Vacuum lamination can be carried out using a commercially available vacuum laminator. For example, a vacuum laminator manufactured by Nikko Materials Co., Ltd., a vacuum press laminator manufactured by Nihon Seiki Co., Ltd., a tumble dryer coater manufactured by Hitachi Industries, and a Hitachi AIC Co., Ltd. Vacuum laminating machine, etc. In this manner, a photosensitive resin composition layer is formed on the circuit board.

<Exposure Step> After the photosensitive film (photosensitive resin composition layer) is provided on the circuit board by the coating and drying step or the lamination step, the photosensitive resin composition layer is passed through the mask pattern. The predetermined portion is irradiated with the active light, and an exposure step of photohardening the photosensitive resin composition layer of the irradiated portion is performed. Examples of the active light include ultraviolet rays, visible light, electron beams, X-rays, and the like, and ultraviolet rays are particularly preferable. The amount of ultraviolet rays to be irradiated is approximately 10 mJ/cm ² to 1000 mJ/cm ² . As the exposure method, a contact exposure method in which a mask pattern is adhered to a printed circuit board is known, and a non-contact exposure method in which the mask is not adhered and exposed using parallel light is known, and any of them can be used. Further, when a support is present on the photosensitive resin composition layer, the support may be exposed to light or the support may be peeled off and exposed.

The solder resist is excellent in resolution because the photosensitive resin composition of the present invention is used. Therefore, for the exposure pattern in the mask pattern, for example, the ratio of the circuit width (line width; L) to the width (spacing; S) between the circuits (L/S) is 100 μm/100 μm or less (that is, the wiring pitch is 200 μm). The following), L/S = 80 μm / 80 μm or less (wiring pitch: 160 μm or less), L/S = 70 μm / 70 μm or less (wiring pitch: 140 μm or less), L/S = 60 μm / 60 μm or less (wiring pitch: 120 μm or less) picture of. In addition, the pitch is not necessarily the same in all of the circuit board.

<Exposure Step> After the exposure step, a support is present on the photosensitive resin composition layer, and after the support is removed, the portion which is not photohardened by wet development or dry development is not The exposed portion is removed and developed to form a pattern.

In the case of the above-described wet development, a developing liquid which is safe and stable, and has good workability, such as an alkaline aqueous solution, an aqueous developing solution, or an organic solvent, can be used as the developing solution, and in particular, the developing step using an aqueous alkali solution is good. Further, as the developing method, a well-known method such as spraying, shaking immersion, painting, and blade coating can be suitably employed.

Examples of the alkaline aqueous solution used as the developing solution include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium hydrogencarbonate; and sodium phosphate; An aqueous solution of an alkali metal pyrophosphate such as an alkali metal phosphate such as potassium phosphate, sodium pyrophosphate or potassium pyrophosphate or an organic base containing no metal ion such as tetraalkylammonium hydroxide, which does not contain a metal ion An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred from the viewpoint of not affecting the semiconductor wafer. For these alkaline aqueous solutions, in order to enhance the development effect, a surfactant, an antifoaming agent, or the like may be added to the developing solution. The pH of the alkaline aqueous solution is preferably in the range of, for example, 8 to 12, and preferably in the range of 9 to 11. Further, the alkali concentration of the alkaline aqueous solution is preferably from 0.1% by mass to 10% by mass. The temperature of the alkaline aqueous solution can be appropriately selected in accordance with the resolution of the photosensitive resin composition layer, and is preferably 20 ° C to 50 ° C.

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

The concentration of the organic solvent is preferably 2% by mass to 90% by mass based on the total amount of the developing liquid. In addition, the temperature of such an organic solvent can be adjusted in accordance with the resolution. Further, such an organic solvent may be used singly or in combination of two or more. The organic solvent-based developing solution used alone may, for example, be 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone or methyl isobutyl. Ketone, γ-butyrolactone.

In the pattern formation, it is also possible to use the above two or more development methods as necessary. The method of development is known as a immersion method, a liquid coating method, a spray method, a high pressure spray method, a brushing, a slap, etc., and a high pressure spray method is suitable for improving the resolution. The spray pressure when using the spray method is preferably 0.05 MPa to 0.3 MPa.

<Thermal hardening (post-baking) step> After the above-mentioned developing step is completed, a thermal hardening (post-baking) step is performed to form a solder resist. The post-baking step may be an ultraviolet irradiation step using a high-pressure mercury lamp or a heating step using a dust-free oven. When the ultraviolet ray is irradiated, the amount of irradiation can be adjusted as necessary, and for example, it can be irradiated with an irradiation amount of about 0.05 J/cm ² to 10 J/cm ² . In addition, the heating condition is preferably selected in accordance with the type and content of the resin component in the photosensitive resin composition, and is preferably heated at 150 to 220 ° C for a period of 20 minutes to 180 minutes, preferably 160 to 200 minutes. °C is heated for a range of 30 minutes to 120 minutes.

<Other Steps> The printed circuit board may further include an opening step and a step of removing the glue after forming the solder resist. These steps can be used for the manufacture of printed circuit boards, which can be implemented by various methods in the industry.

After the solder resist is formed, a solder resist formed on the circuit substrate is subjected to a hole opening step as needed to form a via hole and a through hole. The opening step, for example, may be performed by a well-known method such as a drill, a laser, a plasma, or the like, or a combination of these methods as necessary, to perform a hole opening step using a laser such as a carbon dioxide laser or a YAG laser. It is better.

The degreasing step is a step of performing a degumming treatment. In the opening step, resin residue (slag) is generally adhered to the inside of the formed opening. Such a slag may cause a poor electrical connection, and therefore, in this step, a treatment for removing the slag (degumming treatment) is performed.

The degreasing treatment can be carried out by a dry degumming treatment, a wet degumming treatment, or a combination thereof.

The dry degreasing treatment may, for example, be a gel removal treatment using a plasma. The gel removal treatment using plasma can be carried out using a commercially available plasma degreasing treatment device. Among the commercially available plasma degreasing treatment apparatuses, examples of the use of the printed circuit board for a printed circuit board include a microwave plasma apparatus manufactured by Nissin Co., Ltd., and a normal piezoelectric slurry etching apparatus manufactured by Sekisui Chemical Co., Ltd.

The wet degreasing treatment may, for example, be a degreasing treatment using an oxidizing agent solution. In the case where the degreasing treatment is carried out using the oxidizing agent solution, it is preferred to carry out the swelling treatment by the swelling liquid, the oxidation treatment with the oxidizing agent solution, and the neutralization treatment with the neutralizing liquid. Examples of the swelling liquid include "Swelling Dip Securiganth P" manufactured by Atotech Japan Co., Ltd., "Swelling Dip Securiganth SBU", and the like. The swelling treatment is preferably carried out by immersing the substrate on which the via holes or the like are formed in a swelling liquid heated to 60 to 80 ° C for 5 minutes to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganic acid aqueous solution, and examples thereof include a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The oxidation treatment by the oxidizing agent solution is preferably carried out by immersing the swelled substrate in an oxidizing agent solution heated to 60 to 80 ° C for 10 minutes to 30 minutes. For example, "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd., "Dosing solution Securiganth P", etc., may be mentioned as a commercial item of the alkaline permanganic acid aqueous solution. The neutralization treatment by the neutralization liquid is preferably carried out by immersing the oxidized substrate at a temperature of 30 ° C to 50 ° C for 3 minutes to 10 minutes. The neutralization liquid is preferably an acidic aqueous solution, and a commercially available product is, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd.

In the case where the dry degreasing treatment is combined with the wet degreasing treatment, the dry degreasing treatment may be performed first, or the wet degreasing treatment may be performed first.

The case where the insulating layer is used as the interlayer insulating layer can be carried out in the same manner as in the case of the solder resist, and after the thermal curing step, the opening step, the removing step, and the plating step can be performed.

The plating step is a step of forming a conductor layer on the insulating layer. The conductor layer can be formed by combining electroless plating and electrolytic plating, and a plating resist having a pattern opposite to the conductor layer can be formed, and then the conductor layer can be formed only by electroless plating. The pattern forming method after this can be, for example, a subtractive color method, a semi-additive method, or the like which is well known to those skilled in the art.

[Semiconductor Device] The semiconductor device of the present invention contains a printed circuit board. The semiconductor device of the present invention can be fabricated using the printed circuit board of the present invention.

Examples of the semiconductor device include various semiconductor devices that are supplied to electronic products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, locomotives, automobiles, electric cars, ships, airplanes, etc.).

The semiconductor device of the present invention can be fabricated by mounting a component (semiconductor wafer) at the conduction of a printed circuit board. "Conduit" means "where an electronic signal is transmitted on a printed circuit board" and its location may be either a surface or an embedded location. Further, the semiconductor wafer is not particularly limited as long as it is an electronic circuit element made of a semiconductor.

The method of mounting the semiconductor wafer in the production of the semiconductor device of the present invention is not particularly limited as long as the semiconductor wafer is effectively functioned, and specifically, a wire bonding method, a flip chip mounting method, and a use-free method are exemplified. A method of mounting a bump build-up layer (BBUL), a method of mounting an anisotropic conductive film (ACF), a method of mounting a non-conductive film (NCF), and the like. Here, the "mounting method by bumpless build-up layer (BBUL)" means "a method of mounting a semiconductor wafer directly in a recess of a printed circuit board to connect a semiconductor wafer to a wiring on a printed circuit board" . [Examples]

The invention is more specifically described below in the examples, but the invention is not limited by the examples. In addition, in the following description, "parts" and "%" indicating the amount of articles mean "mass parts" and "mass%" unless otherwise indicated.

(Preparation of Inorganic Filler) Inorganic fillers 1 to 5 are "ADMAFINE" manufactured by Admatech Co., Ltd., "SFP series" manufactured by Electrochemical Industries, Inc., and "SP (H) series manufactured by Nippon Steel & Metals Materials Co., Ltd." The "Sciqas Series" manufactured by Nippon Chemical Industry Co., Ltd. and the "SEAHOSTAR Series" manufactured by Nippon Shokubai Co., Ltd. are separately or combined with an amine-based decane coupling agent (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.), and then classified. Get something. The inorganic filler 6 is obtained by subjecting the surface treatment to the same manner as the inorganic fillers 1 to 5 using alumina ("AZ series" and "AX series" manufactured by Nippon Steel Co., Ltd.). The inorganic filler 7 is obtained by subjecting the inorganic fillers 1 to 5 to a surface treatment similar to the inorganic fillers 1 to 5 using "barium sulfate" ("B series" and "BF series" manufactured by Seiko Chemical Industry Co., Ltd.). In the inorganic fillers 1 to 7, the particle size distribution and the specific surface area were measured by the following methods.

50 mg of the powder of the inorganic filler 1 , 2 g of a nonionic dispersing agent ("T208.5" manufactured by Nippon Oil Co., Ltd.), and 40 g of pure water were weighed into a vial and dispersed by ultrasonic waves for 20 minutes. Determination of the particle size distribution, the calculated average particle diameter, D ₉₀ using a laser diffraction type particle size distribution measuring apparatus (manufactured by Horiba Ltd., LA-950), to detect cell batch (batch cell) manner. The average particle diameter was also calculated in the same manner for the inorganic fillers 2 to 7.

The specific surface area of the inorganic filler 1 was measured using a BET fully automatic specific surface area measuring device (Macsorb HM-1210, manufactured by Mountech Co., Ltd.). The specific surface area was also measured in the same manner for the inorganic fillers 2 to 7. The results of the average particle diameter and specific surface area of each inorganic filler are as follows. Inorganic filler 1: Average particle diameter 0.80μm, D ₉₀ 2.2μm, a specific surface area ² / g inorganic filler 2 4.1m: Average particle diameter 1.75μm, D ₉₀ 4.2μm, a specific surface area ² / g inorganic filler 2.2m 3 : average particle diameter 0.50 μm, D ₉₀ 1.3 μm, specific surface area 6.3 m ² /g inorganic filler 4; average particle diameter 2.10 μm, D ₉₀ 4.7 μm, specific surface area 1.0 m ² /g inorganic filler 5: average particle diameter 0.20 μm, D ₉₀ 0.5 μm, specific surface area 12.0 m ² /g Inorganic filler 6: average particle diameter 0.80 μm, D ₉₀ 2.4 μm, specific surface area 4.0 m ² /g Inorganic filler 7: average particle diameter 0.80 μm, D ₉₀ 2.8μm, specific surface area 5.0m ² /g

(Synthesis Example 1: Synthesis of A-1 component) 1,1'-bis(2,7-diglycidyloxynaphthyl)methane having an epoxy equivalent of 162 ("EXA-4700", Dainippon Ink Chemical Co., Ltd. 162 parts of a flask equipped with a gas introduction tube, a stirring device, a condenser, and a thermometer were placed, and 340 parts of carbitol acetate was added thereto, and dissolved by heating, and then 0.46 parts of hydroquinone and 1 part of triphenylphosphine were added. The mixture was heated to 95 to 105 ° C, and 72 parts of acrylic acid was slowly dropped to carry out a reaction for 16 hours. The reaction product was cooled to 80 to 90 ° C, and 80 parts of tetrahydrophthalic anhydride was added thereto, and the mixture was reacted for 8 hours, followed by cooling. In this manner, a resin solution having a solid acid value of 90 mgKOH/g (nonvolatile content: 70%, hereinafter abbreviated as "A-1") was obtained.

<Examples 1 to 7 and Comparative Examples 1 to 4> Each component was blended according to the blending ratio shown in the following table, and a resin varnish was prepared using a high-speed rotary stirrer. Next, a PET film ("LUMIRROR T6AM", manufactured by Toray Industries, Inc., thickness 38 μm, softening point) prepared by an alcohol resin-based release agent ("AL-5" manufactured by Lintec Co., Ltd.) was prepared as a support. 130 ° C, "release PET"). The prepared resin varnish was uniformly applied to the release PET by a die coater so that the thickness of the dried photosensitive resin composition layer was 40 μm, and dried at 80 ° C to 110 ° C for 6 minutes. A photosensitive film having a support having a photosensitive resin composition layer on the release PET was obtained.

The measurement method and evaluation method in the physical property evaluation are explained.

<Evaluation of Appearance and Flexibility of Film> The appearance of the photosensitive resin composition layer of the photosensitive film with a support produced in the examples and the comparative examples was visually observed. Moreover, the scattering of the resin and the occurrence of cracks at the time of cutting the photosensitive resin composition layer utility knife were visually observed. In addition, the occurrence of cracks when the photosensitive film with a support was bent at 180° was visually evaluated according to the following criteria. ○: Crawling or streaking was not observed, and scattering or cracking of the resin was not observed. ×: Any of shrinkage cavities or streaks, scattering of resin, and cracking were observed.

<Measurement of the average linear thermal expansion coefficient> (Formation of the cured product for evaluation) The photosensitive resin composition layer of the photosensitive film with a support obtained in the examples and the comparative examples was exposed to ultraviolet light of 100 mJ/cm ² to expose Its light hardens. Then, in the entire photosensitive resin composition layer, a 1% by mass aqueous sodium carbonate solution at 30 ° C was used as a developing solution, and spray development was carried out for 2 minutes at a spray pressure of 0.2 MPa. After the spray development, ultraviolet irradiation of 1 J/cm ² was performed, and further heat treatment was performed at 190 ° C for 90 minutes to obtain a cured product. Then, the support was peeled off to prepare a cured product for evaluation.

(Measurement of the average thermal expansion coefficient) The test cured product was cut into a test piece having a width of 5 mm and a length of 15 mm, and subjected to thermomechanical analysis by a tensile weighting method using a thermomechanical analyzer (Thermo P1us, TMA8310, manufactured by Rigaku Co., Ltd.). After the test piece was attached to the above apparatus, it was continuously measured twice under the measurement conditions of a load of 1 g and a temperature increase rate of 5 ° C /min. The average linear thermal expansion coefficient (ppm) at 25 ° C to 150 ° C in the second measurement was calculated.

<Evaluation of resolution and crack resistance> (Formation of laminate for evaluation) A copper layer of a glass epoxy substrate (copper-bonded laminate) in which a copper layer having a thickness of 18 μm is patterned to form a circuit is used. An acid surface treatment agent (CZ8100, manufactured by MEC Corporation) was treated to carry out roughening. Next, the photosensitive resin composition layer of the photosensitive film with a support obtained by the Example and the comparative example was arrange|positioned in contact with the surface of a copper circuit, and the vacuum laminator (V. Lamination is performed to form a laminate in which the copper-clad laminate, the photosensitive resin composition layer, and the support are laminated in this order. The press-bonding conditions were set to a vacuum suction time of 30 seconds, a press-fit temperature of 80 ° C, a press-fit pressure of 0.7 MPa, and a pressurization time of 30 seconds. The laminate was allowed to stand at room temperature for 30 minutes or more, and a circular hole pattern was used on the support of the laminate, and exposure was carried out with ultraviolet rays using a pattern forming apparatus. The exposure pattern is a circular hole in which openings are drawn: 50 μm/60 μm/70 μm/80 μm/90 μm/100 μm, L/S (line width/pitch): 50 μm/50 μm, 60 μm/60 μm, 70 μm/70 μm, 80 μm/80 μm, A quartz glass reticle with a line width and pitch of 90 μm/90 μm and 100 μm/100 μm. After standing at room temperature for 30 minutes, the support was peeled off from the aforementioned laminate. The entire photosensitive resin composition layer on the laminate was subjected to spray development at a spray pressure of 0.2 MPa for 2 minutes using a 1% by mass aqueous solution of sodium carbonate at 30 ° C as a developing solution. After the spray development, ultraviolet irradiation of 1 J/cm ² was performed, and further heat treatment was performed at 180 ° C for 30 minutes to cure the photosensitive resin composition layer, and an insulating layer having an opening was formed on the laminate. This was used as a laminate for evaluation.

(Evaluation of Resolving Property) For the evaluation laminate, a circular hole having a pattern formed by SEM observation (magnification: 1000 times) was measured, and the minimum lead diameter without residue, and the minimum L/S without landfill or peeling were measured. The case where the smallest L/S without resin filling or peeling could not be found was designated as "x". In addition, the L/S shape was evaluated in accordance with the following criteria. ○: Three points of L/S were observed, and there was no peeling or landfill between all L/S. ×: L/S of three points was observed, and resin filling or peeling was observed between L/S of either.

(Evaluation of crack resistance) After the evaluation laminate was exposed to the atmosphere at -65 ° C for 15 minutes, the temperature was raised at a temperature elevation rate of 180 ° C / minute, and then, after exposure for 15 minutes in the atmosphere at 150 ° C, The temperature was lowered at a temperature drop of 180 ° C / min, and this heat cycle was repeated 500 times for testing. After the test, the degree of cracking and peeling of the substrate for evaluation was observed by an optical microscope ("ECLIPSE LV100ND" manufactured by Nikon Corporation), and evaluated according to the following criteria. ○: No cracks and peeling were observed. ×: Cracking and peeling were observed.

Abbreviations in the table are as follows. (A) component, ZAR-2000: bisphenol A type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value: 99 mgKOH/g, solid content concentration: about 70%) ・A-1: A synthesized in Synthesis Example 1. -1 component (nonvolatile content: 70%) (B) component, inorganic filler 1: cerium oxide, average particle diameter 0.80 μm, D ₉₀ 2.2 μm, specific surface area 4.1 m ² /g ・Inorganic filler 2: dioxide矽, average particle diameter 1.75 μm, D ₉₀ 4.2 μm, specific surface area 2.2 m ² /g ・Inorganic filler 3: cerium oxide, average particle diameter 0.50 μm, D ₉₀ 1.3 μm, specific surface area 6.3 m ² /g ・Inorganic Filler 4: cerium oxide, average particle diameter 2.10 μm, D ₉₀ 4.7 μm, specific surface area 1.0 m ² /g ・Inorganic filler 5: cerium oxide, average particle diameter 0.20 μm, D ₉₀ 0.5 μm, specific surface area 12.0 m ² / g · inorganic filler 6: alumina, average particle size of 0.80μm, D ₉₀ 2.4μm, a specific surface area ² / g · inorganic filler 4.0m 7: barium sulphate, average particle size of 0.80μm, D ₉₀ 2.8μm Specific surface area: 5.0 m ² /g (C), Irgacure 819: bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (manufactured by BASF Corporation) (D) component, NC3000H: biphenyl Basic epoxy tree Fat (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 272) ・1031S: tetrahydroxyphenylethane type epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 200) (E) component, DPHA: dipentaerythritol hexaacrylic acid Ester (manufactured by Nippon Kayaku Co., Ltd., acrylic acid equivalent: about 96) (F) component, EDGAc: ethyl diglycol acetate, MEK: methyl ethyl ketone, (B) component content: solid of photosensitive resin composition The content of the component (B) when the total amount of the component is 100% by mass

As is apparent from the results of the above-mentioned table, in the case of using the photosensitive resin composition of the present invention, the appearance, flexibility, resolution, and crack resistance of the film were low, and the average linear thermal expansion coefficient was low.

On the other hand, in Comparative Example 1 in which the content of the inorganic filler was more than 85% by mass, the appearance, flexibility, and resolution of the film were poor, and it was not an article which can be used as a photosensitive resin composition. In Comparative Example 2 in which the content of the inorganic filler was less than 60% by mass, the average linear thermal expansion coefficient was high. Further, it is not suitable for use as a photosensitive resin composition because of poor crack resistance. In Comparative Example 3 in which the inorganic filler having an average particle diameter of less than 0.5 μm and a specific surface area of more than 10 m ² /g was not sufficiently filled with the component (B), the average linear thermal expansion coefficient was high. Further, the film has poor appearance, flexibility, resolution, and crack resistance, and is not an article that can be used as a photosensitive resin composition. In Comparative Example 4 using an inorganic filler having a specific surface area of less than 1.4 m ² /g, since the resolution was poor, the minimum pore diameter was more than 100 μm, and it was not an article which can be used as a photosensitive resin composition.

In each of the examples, it was confirmed that even when the components (E) to (F) were not contained, although the degree was different, the same results as those of the above examples were summarized.

Claims (12)

A photosensitive resin composition containing a photosensitive resin composition of the following components: (A) a resin containing an ethylenically unsaturated group and a carboxyl group, and (B) an average particle diameter of 0.5 μm or more and 2.5 μm or less, specific surface area It is an inorganic filler of 1.4 m ² /g or more and 10 m ² /g or less, (C) photopolymerization initiator, and (D) epoxy resin, and the solid content of the photosensitive resin composition is 100. When the mass is %, the content of the component (B) is 60% by mass or more and 85% by mass or less. The photosensitive resin composition of claim 1, wherein the photosensitive resin composition is photocured, and the cured product which is thermally cured at 190 ° C for 90 minutes has an average linear thermal expansion coefficient of from 5 ppm to 45 ppm at 25 ° C to 150 ° C. The photosensitive resin composition of claim 1, wherein the component (A) has a naphthalene skeleton. The photosensitive resin composition of claim 1, wherein the component (A) is an epoxy (meth) acrylate containing an acid-modified naphthalene skeleton. The photosensitive resin composition of claim 1, wherein the component (D) contains at least one of a biphenyl type epoxy resin and a tetraphenylethane type epoxy resin. The requested item of a photosensitive resin composition, wherein the specific surface area (B) component is 2m ² / g or more 7m ² / g or less. The photosensitive resin composition of claim 1, wherein the component (B) contains cerium oxide. A photosensitive film containing the photosensitive resin composition according to any one of claims 1 to 7. A photosensitive film having a support comprising a support and a photosensitive resin composition layer containing the photosensitive resin composition according to any one of claims 1 to 7 provided on the support. A printed circuit board comprising an insulating layer formed of a cured product of the photosensitive resin composition according to any one of claims 1 to 7. The printed circuit board of claim 10, wherein the insulating layer is a solder resist. A semiconductor device comprising the printed circuit board of claim 10.