JP6705412B2 - Photosensitive resin composition - Google Patents

Description

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

In a printed wiring board, a solder resist may be provided as a permanent protective film for preventing the solder from adhering to a portion where the solder is unnecessary and for preventing the circuit board from corroding. As the solder resist, it is common to use a photosensitive resin composition as described in Patent Document 1, for example.

JP, 2011-164304, A

Photosensitive resin compositions for solder resist generally have resolution, insulation, solder heat resistance, gold plating resistance, moist heat resistance, crack resistance (TCT resistance), and super-accelerated high temperature between fine wiring lines. HAST resistance to high humidity life test (HAST) is required. In recent years, higher performance has been demanded for solder resists in response to higher density of printed wiring boards. In particular, the demand for crack resistance is increasing year by year, and it is important to have further durability.

In order to increase crack resistance, for example, a method of highly filling the photosensitive resin composition with an inorganic filler is conceivable, but the adhesiveness with an adherend is lowered, or the light transmission is not sufficient, so that the via There is a possibility that the sensitivity of the bottom may deteriorate and undercut may occur, or the light may not be sufficiently opened due to halation of light.

From the viewpoint of productivity, solder resists are required to be resistant to cracking during handling and to be resistant to cracking and resin scattering during cutting of the solder resist.

An object of the present invention is to provide a photosensitive resin composition which is excellent in crack resistance, can obtain a cured product having a low average linear thermal expansion coefficient, and has excellent film appearance, flexibility, and resolution when formed into a film. An object is to provide a photosensitive film, a photosensitive film with a support, a printed wiring board, and a semiconductor device obtained by using the photosensitive resin composition.

As a result of intensive studies to solve the above problems, the present inventors have included an inorganic filler having a predetermined average particle diameter and a predetermined specific surface area in a photosensitive resin composition, thereby providing resolution, crack resistance, and Further, they have found that the appearance and flexibility of a film when formed into a film are improved, and have completed the present invention.

That is, the present invention includes the following contents.
[1] (A) a resin containing an ethylenically unsaturated group and a carboxyl group,
(B) An inorganic filler having an average particle size 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,
A photosensitive resin composition containing (C) a photopolymerization initiator and (D) an epoxy resin,
The content of the component (B) is 60% by mass or more and 85% by mass or less when the total solid content of the photosensitive resin composition is 100% by mass.
[2] The average linear thermal expansion coefficient at 25° C. to 150° C. of the cured product obtained by photo-curing the photosensitive resin composition at 190° C. for 90 minutes is 10 ppm or more and 45 ppm or less, [1] The photosensitive resin composition according to item 1.
[3] The photosensitive resin composition according to [1] or [2], in which 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 acid-modified naphthalene skeleton-containing epoxy (meth)acrylate.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein the component (D) contains at least either a biphenyl type epoxy resin or a tetraphenylethane type epoxy resin.
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the specific surface area of the component (B) is 2 m ² /g or more and 7 m ² /g or less.
[7] The photosensitive resin composition according to any one of [1] to [6], wherein the component (B) contains silica.
[8] A photosensitive film containing the photosensitive resin composition according to any one of [1] to [7].
[9] A photosensitive material with a support, which has a support and a photosensitive resin composition layer provided on the support and containing the photosensitive resin composition according to any one of [1] to [7]. Sex film.
[10] A printed wiring board including an insulating layer formed from the cured product of the photosensitive resin composition according to any one of [1] to [7].
[11] The printed wiring board according to [10], wherein the insulating layer is a solder resist.
[12] A semiconductor device including the printed wiring board according to [10] or [11].

According to the present invention, it is possible to obtain a cured product having excellent crack resistance and a low average linear thermal expansion coefficient, and a photosensitive resin composition having excellent film appearance, flexibility, and resolution when formed into a film. Articles: A photosensitive film, a photosensitive film with a support, a printed wiring board, and a semiconductor device obtained by using the photosensitive resin composition can be provided.

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

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

By including the components (A) to (D) in the photosensitive resin composition, a cured product having excellent crack resistance and a low average linear thermal expansion coefficient can be obtained, and the cured product can be formed into a film. It is possible to obtain a photosensitive resin composition having excellent appearance, flexibility and resolution. The photosensitive resin composition may further contain (E) a reactive diluent and (F) an organic solvent, if necessary. Hereinafter, each component contained in the photosensitive resin composition will be described in detail.

<(A) Resin containing ethylenically 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 maleimide group, a nadiimide group, and a (meth)acrylic group, which are reactive to photoradical polymerization. From the viewpoint of, a (meth)acrylic group is preferable. The “(meth)acrylic group” refers to a methacrylic group and an acrylic group.

There are no particular restrictions on the component (A) as long as it is a compound having an ethylenically unsaturated group and a carboxyl group and capable of radical photopolymerization and alkali development. A resin having a combination of one or more ethylenically unsaturated groups is preferable.

One embodiment of the resin containing an ethylenically unsaturated group and a carboxyl group is an acid-modified unsaturated epoxy ester resin obtained by reacting an epoxy compound with an unsaturated carboxylic acid and further reacting with an acid anhydride. Specifically, an acid-modified 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 reacting the unsaturated epoxy ester resin with an acid anhydride.

As the epoxy compound, any compound having an epoxy group in the molecule can be used. For example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin. , Bisphenol S type epoxy resin, bisphenol F type epoxy resin reacted with epichlorohydrin, and modified bisphenol F type epoxy resin such as modified bisphenol F type epoxy resin; biphenol type epoxy resin, tetramethyl biphenol type, etc. Biphenol type epoxy resin; novolac type epoxy resin such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type novolac type epoxy resin, alkylphenol novolac type epoxy resin; bisphenol AF type epoxy resin and perfluoroalkyl type epoxy resin Fluorine-containing epoxy resin such as resin; naphthalene type epoxy resin, dihydroxynaphthalene type epoxy resin, polyhydroxybinaphthalene type epoxy resin, naphthol type epoxy resin, binaphthol type epoxy resin, naphthylene ether type epoxy resin naphthol novolac type epoxy resin, poly Epoxy resin having naphthalene skeleton such as naphthalene type epoxy resin obtained by condensation reaction of hydroxynaphthalene and aldehydes (naphthalene skeleton-containing epoxy resin); bixylenol type epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin Tert-butyl-catechol type epoxy resin; epoxy resin containing condensed ring skeleton such as anthracene type epoxy resin; glycidyl amine type epoxy resin; glycidyl ester type epoxy resin; biphenyl type epoxy resin; linear aliphatic epoxy resin; butadiene Epoxy resin having structure; alicyclic epoxy resin; heterocyclic epoxy resin; spiro ring-containing epoxy resin; cyclohexanedimethanol type epoxy resin; trimethylol type epoxy resin; tetraphenylethane type epoxy resin; polyglycidyl (meth)acrylate , A glycidyl group-containing acrylic resin such as a copolymer of glycidyl methacrylate and acrylic ester; a fluorene type epoxy resin; a halogenated epoxy resin and the like.

From the viewpoint of reducing the average coefficient of linear thermal expansion, an epoxy resin containing an aromatic skeleton is preferable. Here, the aromatic skeleton is a concept including polycyclic aromatic and aromatic heterocycles. Among them, 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 resin, and a glycidyl ester type epoxy resin are preferable. Among them, 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 is higher, and the average linear thermal expansion coefficient of the cured product is further decreased. A skeleton-containing epoxy resin, an epoxy resin containing a condensed ring skeleton, and a biphenyl type epoxy resin are more preferable, and a naphthalene skeleton-containing epoxy resin is further preferable. The naphthalene skeleton-containing epoxy resin is preferably a dihydroxynaphthalene type epoxy resin, a polyhydroxybinaphthalene type epoxy resin, or a naphthalene type epoxy resin obtained by a condensation reaction of polyhydroxynaphthalene and aldehydes.

Examples of the dihydroxynaphthalene-type epoxy resin include 1,3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, 1,6-diglycidyloxynaphthalene, and 2,3-diglycidyloxynaphthalene. Examples thereof include glycidyloxynaphthalene, 2,6-diglycidyloxynaphthalene, and 2,7-diglycidyloxynaphthalene.

Examples of the polyhydroxybinaphthalene type epoxy resin include 1,1′-bi-(2-glycidyloxy)naphthyl, 1-(2,7-diglycidyloxy)-1′-(2′-glycidyloxy)binaphthyl, 1,1'-bi-(2,7-diglycidyloxy)naphthyl and the like can be mentioned.

Examples of the naphthalene-type epoxy resin obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes include 1,1′-bis(2,7-diglycidyloxynaphthyl)methane and 1-(2,7-diglycidyloxynaphthyl). )-1'-(2'-glycidyloxynaphthyl)methane and 1,1'-bis(2-glycidyloxynaphthyl)methane.

Among these, a polyhydroxybinaphthalene type epoxy resin having two or more naphthalene skeletons in one molecule and a naphthalene type epoxy resin obtained by a condensation reaction of polyhydroxynaphthalene and aldehydes are preferable, and an epoxy in one molecule is particularly preferable. 1,1′-bis(2,7-diglycidyloxynaphthyl)methane having 3 or more groups, 1-(2,7-diglycidyloxynaphthyl)-1′-(2′-glycidyloxynaphthyl)methane, 1-(2,7-diglycidyloxy)-1'-(2'-glycidyloxy)binaphthyl and 1,1'-bi-(2,7-diglycidyloxy)naphthyl are added to the average linear thermal expansion coefficient. It is preferable because it has excellent heat resistance.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, etc. These may be used alone or in combination of two or more. Among them, acrylic acid and methacrylic acid are preferable from the viewpoint of improving the photocurability of the photosensitive resin composition. In the present specification, the epoxy ester resin, which is a reaction product of the above epoxy compound and (meth)acrylic acid, may be referred to as “epoxy (meth)acrylate”, and the epoxy group of the epoxy compound is Substantially disappeared by the reaction with (meth)acrylic acid. “(Meth)acrylate” refers to methacrylate and acrylate. Acrylic acid and methacrylic acid may be collectively referred to as “(meth)acrylic acid”.

Examples of the acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. Examples thereof include anhydrides, and any one of these may be used alone or two or more of them may be used in combination. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferable from the viewpoint of improving the resolution and insulation reliability of the cured product.

In obtaining an acid-modified unsaturated epoxy ester resin, an unsaturated carboxylic acid and an epoxy resin are reacted 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. Good. Moreover, you may use a solvent and a polymerization inhibitor as needed.

As the acid-modified unsaturated epoxy ester resin, acid-modified epoxy (meth)acrylate is preferable. The “epoxy” in the acid-modified unsaturated epoxy ester resin represents a structure derived from the above-mentioned epoxy compound. For example, "acid-modified bisphenol-type epoxy (meth)acrylate" means an acid-modified unsaturated epoxy ester resin obtained by using bisphenol-type epoxy resin as an epoxy compound and (meth)acrylic acid as an unsaturated carboxylic acid. Refers to. The preferable range of the acid-modified epoxy (meth)acrylate is derived from the preferable range of the epoxy compound. That is, the acid-modified unsaturated epoxy ester resin is preferably an acid-modified naphthalene skeleton-containing epoxy (meth)acrylate from the viewpoint of increasing the glass transition temperature of the cured product of the resin composition and decreasing the average linear thermal expansion coefficient. The acid-modified naphthalene skeleton-containing epoxy (meth)acrylate is a compound obtained by reacting a reaction product of a naphthalene type epoxy resin and (meth)acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. ..

As such an acid-modified unsaturated epoxy ester resin, a commercially available product can be used, and specific examples thereof include "ZAR-2000" manufactured by Nippon Kayaku Co., Ltd. (of bisphenol A type epoxy resin, acrylic acid, and succinic anhydride). Reaction product), "ZFR-1491H", "ZFR-1533H" (reaction product of bisphenol F type epoxy resin, acrylic acid, and tetrahydrophthalic anhydride), "PR-300CP" manufactured by Showa Denko KK (cresol novolac type epoxy) Resin, acrylic acid, and a reaction product of an acid anhydride) and the like. These may be used alone or in combination of two or more.

As another embodiment of the resin containing an ethylenically unsaturated group and a carboxyl group, an ethylenically unsaturated group-containing epoxy compound is added to a (meth)acrylic resin having a structural unit obtained by polymerizing (meth)acrylic acid. An unsaturated modified (meth)acrylic resin in which an ethylenically unsaturated group is introduced by reaction is exemplified. Examples of the ethylenically unsaturated group-containing epoxy compound include glycidyl methacrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth)acrylate. Furthermore, it is also possible to react an acid anhydride with the hydroxyl group generated when the unsaturated group is introduced. As the acid anhydride, those similar to the above-mentioned acid anhydride can be used, and the preferable range is also the same.

As such an unsaturated modified (meth)acrylic resin, a commercially available product can be used, and specific examples thereof include "SPC-1000" and "SPC-3000" manufactured by Showa Denko KK and "Cyclomer" manufactured by Daicel Ornex. P(ACA)Z-250", "Cyclomer P(ACA)Z-251", "Cyclomer P(ACA)Z-254", "Cyclomer P(ACA)Z-300", "Cyclomer P( ACA) Z-320" and the like.

The weight average molecular weight of the component (A) is preferably 1000 or more, more preferably 1500 or more, and further preferably 2000 or more, from the viewpoint of film-forming property. From the viewpoint of developability, the upper limit is preferably 10,000 or less, more preferably 8,000 or less, and further preferably 7500 or less. The weight average molecular weight is a polystyrene equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

From the viewpoint of improving the alkali developability of the photosensitive resin composition, the acid value of the component (A) is preferably 0.1 mgKOH/g or more, and 0.5 mgKOH/g or more. Is more preferable and 1 mgKOH/g or more is further preferable. On the other hand, the acid value is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, from the viewpoint of suppressing dissolution of the fine pattern of the cured product by development and improving insulation reliability. It is more preferably 100 mgKOH/g or less. Here, the acid value is 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, about 1 g of the measured resin solution is precisely weighed, and then 30 g of acetone is added to the resin solution to uniformly dissolve the resin solution. Next, an appropriate amount of phenolphthalein, which is an indicator, is added to the solution, and titration is performed using a 0.1N KOH aqueous solution. Then, the acid value is calculated by the following formula.
Formula: A=10×Vf×56.1/(Wp×I)

In the above formula, A represents an acid value (mgKOH/g), Vf represents a titration amount (mL) of KOH, Wp represents a measured resin solution mass (g), and I represents a nonvolatile content of the measured resin solution. Represents the ratio (mass %).

In the production of the component (A), from the viewpoint of improving storage stability, the ratio of the number of moles of epoxy groups in the epoxy resin to the number of moles of total carboxyl groups of unsaturated carboxylic acid and acid anhydride is 1 : The range of 0.8 to 1.3 is preferable, and the range of 1:0.9 to 1.2 is more preferable.

From the viewpoint of improving alkali developability, the component (A) preferably has a content of 5% by mass or more, and 8% by mass or more, when the total solid content of the photosensitive resin composition is 100% by mass. And more preferably 10% by mass or more. From the viewpoint of improving heat resistance, the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.

<(B) Inorganic filler having an average particle size 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>
The photosensitive resin composition contains (B) an inorganic filler having an average particle size 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. By containing the component (B), it is possible to provide a photosensitive resin composition that can obtain a cured product having a low average coefficient of linear thermal expansion.

The material of the inorganic filler is not particularly limited, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphate tungstate, and the like. Among these, silica, alumina and barium sulfate are preferable, and silica is particularly preferable. Further, spherical silica is preferable as the silica. The inorganic fillers may be used alone or in combination of two or more.

The average particle size of the inorganic filler is 0.5 μm or more, preferably 0.6 μm or more, and more preferably 0.7 μm or more, from the viewpoint of obtaining a cured product having a low average coefficient of linear thermal expansion. The upper limit of the average particle size is 2.5 μm or less, preferably 2 μm or less, and more preferably 1.8 μm or less, from the viewpoint of obtaining excellent resolution. Examples of commercially available silica having such an average particle diameter include "Admafine" manufactured by Admatechs, "SFP series" manufactured by Denki Kagaku Kogyo Co., Ltd., "SP(H) series" manufactured by Nippon Steel & Sumikin Materials Co., Ltd., Examples include "Siqas series" manufactured by Sakai Chemical Industry Co., Ltd., "Seahoster series" manufactured by Nippon Shokubai Co., Ltd., and commercially available products of alumina include "AZ series" and "AX series" manufactured by Nippon Steel & Sumikin Materials Co., Ltd. Examples of commercially available barium sulfate include "B series" and "BF series" manufactured by Sakai Chemical Industry Co., Ltd.

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 is created on a volume basis by a laser diffraction/scattering particle size distribution measuring device, and the particle size at which the cumulative frequency is 50% (d50) is taken as the average particle size. be able to. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction/scattering particle size distribution measuring device, "LA-500" manufactured by Horiba Ltd. or "SALD-2200" manufactured by Shimadzu Corp. 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, more preferably 0.8 μm or more from the viewpoint of obtaining a cured product having a low average coefficient of linear thermal expansion. , And more preferably 1 μm or more. The upper limit of D ₉₀ is 5.5 μm or less, preferably 5 μm or less, and more preferably 4.5 μm or less from the viewpoint of obtaining excellent resolution. D90 can be measured by the same method as the average particle size.

The inorganic filler having a desired average particle diameter can be obtained by classifying the inorganic filler with a classifier or the like.

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 more preferably 2 m ² /g or more, from the viewpoint of obtaining excellent resolution. The upper limit of the specific surface area is 10 m ² /g or less, preferably 9 m ² /g or less, more preferably 8 m ² /g or less, still more preferably 7 m ² /g or less, from the viewpoint of obtaining excellent crack resistance. It is 5 m ² /g or less.

The specific surface area of the inorganic filler can be measured according to the method described later (Preparation of inorganic filler).

The inorganic filler is an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane compound, an organosilazane compound, or a titanate from the viewpoint of enhancing the moisture resistance and dispersibility. It is preferably treated with at least one surface treatment agent such as a system coupling agent. Examples of commercially available surface treatment 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 Industry "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Industry "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Industry "SZ-31" ( Hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent), and the like.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, 1 mg/m ² or less is preferable, 0.8 mg/m ² or less is more preferable, and 0.5 mg/m ² or less is further from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish or the melt viscosity in the sheet form. preferable.

The amount of carbon per unit surface area of the inorganic filler can be measured after cleaning the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

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

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

The component (C) is not particularly limited, but for example, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl) ) Methyl]-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and other α-aminoalkylphenone systems Photopolymerization initiator; oxime ester-based photopolymerization initiator such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) Benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl-(2 , 4,6-Trimethylbenzoyl)phenyl phosphinate, 4,4′-bis(diethylamino)benzophenone, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1 Examples include -[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxand. Also, a sulfonium salt-based photopolymerization initiator or the like can be used. These may be used alone or in combination of two or more.

Furthermore, the photosensitive resin composition is combined with the component (C) to serve as a photopolymerization initiation aid, N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-. It may contain tertiary amines such as dimethylaminobenzoate, triethylamine and triethanolamine, and may also contain photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones and thioxanthones. Good. These 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", and "Irgacure OXE-01", "IrgacureOX", Irgacure Ox, manufactured by BASF. "N-1919" manufactured by ADEKA and the like can be mentioned.

The content of the component (C) is preferably, when the total solid content of the photosensitive resin composition is 100% by mass, from the viewpoint of sufficiently photo-curing the photosensitive resin composition and improving insulation reliability. It is 0.01% by mass or more, more preferably 0.03% by mass or more, and further preferably 0.05% by mass or more. On the other hand, the upper limit is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.3% by mass or less, from the viewpoint of suppressing a decrease in resolution due to excessive sensitivity.

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

Examples of the component (D) include fluorine-containing epoxy resins such as bisphenol AF type epoxy resin and perfluoroalkyl type epoxy resin; bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol S type epoxy resin; bixylenol type Epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin; naphthol novolac type epoxy resin; phenol novolac type epoxy resin; tert-butyl-catechol type epoxy resin; naphthalene type epoxy resin; naphthol type epoxy resin; anthracene type epoxy resin Resin; Glycidylamine type epoxy resin; Glycidyl ester type epoxy resin; Cresol novolac type epoxy resin; Biphenyl type epoxy resin; Linear aliphatic epoxy resin; Epoxy resin having butadiene structure; Alicyclic epoxy resin, fat having ester skeleton Cyclic epoxy resin; Heterocyclic epoxy resin; Spiro ring-containing epoxy resin; Cyclohexanedimethanol type epoxy resin; Naphthylene ether type epoxy resin; Trimethylol type epoxy resin; Tetraphenylethane type epoxy resin, halogenated epoxy resin, etc. From the viewpoint of improving adhesion, a bisphenol F type epoxy resin and a biphenyl type epoxy resin are preferable, and a biphenyl type epoxy resin is more preferable. Further, from the viewpoint of improving heat resistance, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, naphthylene ether type epoxy resin, tetraphenylethane type epoxy resin are preferable, and tetraphenylethane type epoxy resin is more preferable. .. The epoxy resins may be used alone or in combination of two or more. From the viewpoint of improving adhesion and heat resistance, the component (D) preferably contains at least one of a biphenyl type epoxy resin and a tetraphenylethane type epoxy resin.

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, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. As the component (E), two or more epoxy resins may be used in combination.

Specific examples of the epoxy resin include "HP4032", "HP4032D", "HP4032SS", "HP4032H" (naphthalene type epoxy resin) manufactured by DIC, "828US", "jER828EL" (bisphenol A type) manufactured by Mitsubishi Chemical Corporation. Epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (A mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "YD-8125G" (bisphenol A type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "EX-721" (glycidyl ester) manufactured by Nagase Chemtex Co., Ltd. Type epoxy resin), "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel, "PB-3600" (epoxy resin having a butadiene structure), "ZX1658" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ZX1658GS" (liquid 1,4-glycidylcyclohexane), "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "E-7432", "E-7632" (perfluoroalkyl type epoxy) manufactured by Daikin Industries, Ltd. Resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy) manufactured by DIC. Resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4". , "EXA-7331-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. , "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "ESN485" (naphthol novolac type epoxy resin), "YSLV-80XY" (tetramethylbisphenol F type epoxy resin), "YX4000H" manufactured by Mitsubishi Chemical Corporation, "Y L6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemicals, Mitsubishi Chemical "YL7800" (fluorene type epoxy resin), Mitsubishi Chemical "1010" (solid bisphenol A type epoxy resin), "1031S" (tetraphenylethane type epoxy resin), "YL7760" (bisphenol AF type) Epoxy resin) and the like.

The content of the component (D) is preferably 1% by mass or more when the total solid content of the photosensitive resin composition is 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good tensile breaking strength and insulation reliability. , More preferably 5% by mass or more, further preferably 8% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 25 mass% or less, more preferably 20 mass% or less, and further preferably 15 mass% or less.

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, even more preferably 80 to 2000, and even more preferably 110 to 1000. Within this range, the cross-linking density of the cured product of the photosensitive resin composition will be sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent can be measured according to JIS K7236 and is the mass of the resin containing 1 equivalent of epoxy group.

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and further preferably 400 to 1500. 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 component (E), photoreactivity can be improved. As the component (E), for example, a photosensitive (meth)acrylate compound which has one or more (meth)acryloyl groups in one molecule and is liquid, solid or semi-solid at room temperature can be used. Room temperature refers to about 25°C. The "(meth)acryloyl group" refers to an acryloyl group and a methacryloyl group.

Typical photosensitive (meth)acrylate compounds include, for example, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate, and glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol. Mono or diacrylates, N,N-dimethylacrylamide, acrylamides such as N-methylolacrylamide, aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate, trimethylolpropane, pentaerythritol, and dipentaerythritol. Polyhydric acrylates of polyhydric alcohols or adducts of 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, trimethylolpropane Examples thereof include epoxy acrylates derived from glycidyl ethers such as triglycidyl ether, melamine acrylates, and/or methacrylates corresponding to the above acrylates. Among these, polyvalent acrylates or polyvalent methacrylates are preferable, and examples of trivalent acrylates or methacrylates include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and trimethylolpropane. EO-added tri(meth)acrylate, glycerin PO-added tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetrafurfuryl alcohol oligo(meth)acrylate, ethylcarbitol oligo(meth)acrylate, 1,4-butanediol Oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol hexa(meth) ) Acrylate, (meth)acrylic acid ester of N,N,N′,N′-tetrakis(β-hydroxyethyl)ethyldiamine and the like, and tri(2- or higher) acrylates or methacrylates are 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)) Mention may be made of phosphoric acid triester (meth)acrylates such as acryloyloxyethyl)phosphate. These photosensitive (meth)acrylate compounds may be used alone or in combination of two or more.

The content when the component (E) is blended is from the viewpoint of accelerating photocuring and suppressing stickiness when it is a cured product, when the total solid content of the photosensitive resin composition is 100% by mass. , 0.5 mass% to 10 mass% is preferable, and 2 mass% to 8 mass% is more preferable.

<(F) Organic solvent>
The photosensitive resin composition may further contain (G) an organic solvent. By incorporating the component (G), the viscosity of the varnish can be adjusted. Examples of the organic solvent (G) 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, triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, ethyl diglycol acetate, Examples thereof include aliphatic hydrocarbons such as octane and decane, petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These may be used alone or in combination of two or more. The content when an organic solvent is used can be appropriately adjusted from the viewpoint of the coating property of the photosensitive resin composition.

<(G) Other additives>
The photosensitive resin composition may further contain (G) and other additives to the extent that the object of the present invention is not impaired. (G) Other additives include, for example, fine particles of thermoplastic resin, organic filler, melamine, organic bentonite, phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, titanium oxide, carbon black, Colorants such as naphthalene black, hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, polymerization inhibitors such as pyrogallol, Benton, thickeners such as montmorillonite, silicone type, fluorine type, vinyl resin type defoaming agent, Brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus compounds, flame retardants such as aromatic condensed phosphoric acid esters, halogen-containing condensed phosphoric acid esters, phenolic curing agents, cyanate ester curing agents, etc. Various additives such as a cured resin can be added.

In the photosensitive resin composition, the above-mentioned components (A) to (D) are mixed as essential components, the above-mentioned components (E) to (G) are appropriately mixed as optional components, and if necessary, three rolls, A resin varnish can be produced by kneading or stirring with a kneading means such as a ball mill, a bead mill, a sand mill or a stirring means such as a super mixer or a planetary mixer.

<Physical properties and applications of photosensitive resin composition>
A cured product obtained by photocuring the photosensitive resin composition of the present invention and then thermally curing it at 190° C. for 90 minutes exhibits a characteristic that the average linear thermal expansion coefficient is low. That is, it provides an insulating layer and a solder resist having a low average coefficient of linear thermal expansion. The average coefficient of linear thermal expansion is preferably 45 ppm or less, more preferably 44 ppm or less, still more preferably 43 ppm or less and 42 ppm or less. The lower limit is not particularly limited, but may be 10 ppm or more. The average coefficient of linear thermal expansion can be measured according to the method described in <Measurement of average coefficient of linear expansion> 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, it has excellent resolution even if the content of the component (B) is large. Shows the characteristics. Therefore, the minimum via diameter with no residue is preferably 100 μm or less, more preferably 90 μm or less, still more preferably 80 μm or less, 70 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more. Further, because of excellent resolution, there is usually no resin embedding or peeling between L/S (line/space). The lower limit is not particularly limited, but may be 1 μm/1 μm or more. The resolution can be evaluated according to the method described in <Evaluation of resolution and crack resistance> described later.

The cured product obtained by photocuring the photosensitive resin composition of the present invention and then thermally curing it at 190° C. for 90 minutes exhibits excellent crack resistance. That is, it provides an insulating layer and a solder resist having excellent crack resistance. Even if the temperature rising test between −65° C. and 150° C. is repeated 500 times, cracks and peeling are not usually recognized. The crack resistance can be evaluated according to the method described in <Evaluation of resolution and crack resistance> described later.

The use of the photosensitive resin composition of the present invention is not particularly limited, but a photosensitive film, a photosensitive film with a support, an insulating resin sheet such as a prepreg, a circuit board (a laminated board application, a multilayer printed wiring board application, etc.), It can be used in a wide range of applications where a photosensitive resin composition is required, such as a solder resist, an underfill material, a die bonding material, a semiconductor encapsulating material, a hole filling resin and a component filling resin. Among them, a photosensitive resin composition for an insulating layer of a printed wiring board (a printed wiring board having a cured product of the photosensitive resin composition as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a photosensitive resin composition A printed wiring board having a cured product as an interlayer insulating layer), a photosensitive resin composition for forming a plating (a printed wiring board having a plating formed on the cured product of the photosensitive resin composition), and a photosensitive resin composition for a solder resist (Printed wiring board using a cured product of a photosensitive resin composition as a solder resist).

[Photosensitive film]
The photosensitive resin composition of the present invention can be applied as a resin varnish on a supporting substrate and dried with an organic solvent to form a photosensitive resin composition layer, thereby forming a photosensitive film. Further, a photosensitive film previously formed on a support may be laminated on a support substrate and used. The photosensitive film can be laminated on various supporting substrates. Examples of the supporting substrate include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like.

[Photosensitive film with support]
The photosensitive resin composition of the present invention can be suitably used in the form of a photosensitive film with a support, in which a photosensitive resin composition layer is formed on a support. That is, the photosensitive film with a support includes a support and a photosensitive resin composition layer formed of the photosensitive resin composition of the present invention, which is provided on the support.

Examples of the support include a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a polyvinyl alcohol film, a triacetyl acetate film, and the like, and a polyethylene terephthalate film is particularly preferable.

Examples of commercially available supports include product names "Alphan MA-410" and "E-200C" manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and product name "PS-25" manufactured by Teijin Ltd. Examples thereof include polyethylene terephthalate films such as PS series, but are not limited to these. In order to facilitate the removal of the photosensitive resin composition layer, these supports are preferably coated on the surface with a release agent such as a silicone coating agent. The thickness of the support is preferably in the range of 5 μm to 50 μm, and more preferably in the range of 10 μm to 25 μm. By setting the thickness to 5 μm or more, it is possible to prevent the support from breaking at the time of peeling the support before development, and by setting the thickness to 50 μm or less, it is possible to prevent the exposure from above the support. The resolution can be improved. Also, a low fish eye support is preferred. Here, the fish eye means that when a material is heat-melted, kneaded, extruded, biaxially stretched, or cast to produce a film, foreign matter, undissolved material, oxidative deterioration material, etc. are taken into the film. It is a thing.

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

By protecting the photosensitive resin composition layer side of the photosensitive film with a support with a protective film, it is possible to prevent dust and the like from adhering to the surface of the photosensitive resin composition layer or scratches. As the protective film, a film made of the same material as the above support can be used. Although the thickness of the protective film is not particularly limited, it is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and further preferably in the range of 10 μm to 30 μm. When the thickness is 1 μm or more, the handleability of the protective film can be improved, and when the thickness is 40 μm or less, the cost efficiency tends to be improved. The protective film preferably has a smaller adhesive force between the photosensitive resin composition layer and the protective film than the adhesive force between the photosensitive resin composition layer and the support.

The photosensitive film with a support of the present invention is, for example, a resin varnish prepared by dissolving the photosensitive resin composition of the present invention in an organic solvent, and coating the resin varnish on a support, followed by heating or blowing hot air. Can be manufactured by drying the organic solvent to form a photosensitive resin composition layer. Specifically, first, after completely removing the bubbles in the photosensitive resin composition by a vacuum defoaming method or the like, the photosensitive resin composition is applied on a support, and the solvent is removed by a hot air oven or a far infrared oven. The support-containing photosensitive film can be produced by removing and drying, and then laminating a protective film on the obtained photosensitive resin composition layer, if necessary. The specific drying conditions vary depending on the curability of the photosensitive resin composition and the amount of organic solvent in the resin varnish, but in the resin varnish containing 30% by mass to 60% by mass of the organic solvent, 80°C to 120°C. Can be dried in 3 to 13 minutes. The amount of the residual organic solvent in the photosensitive resin composition layer is preferably 5% by mass or less with respect to 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 more preferable that the amount is 2% by mass or less. Those skilled in the art can appropriately set suitable drying conditions by a simple experiment. The thickness of the photosensitive resin composition layer is preferably in the range of 5 μm to 500 μm from the viewpoint of improving handleability and suppressing deterioration of sensitivity and resolution inside the photosensitive resin composition layer. The range of 10 μm to 200 μm is more preferable, the range of 15 μm to 150 μm is more preferable, the range of 20 μm to 100 μm is even more preferable, and the range of 20 μm to 60 μm is particularly preferable.

The coating method of the photosensitive resin composition, for example, gravure coating method, micro gravure coating method, reverse coating method, kiss reverse coating method, die coating method, slot die method, lip coating method, comma coating method, blade coating method, The roll coating method, knife coating method, curtain coating method, chamber gravure coating method, slot orifice method, spray coating method, dip coating method and the like can be mentioned.
The photosensitive resin composition may be applied several times, may be applied once, or may be applied by combining a plurality of different methods. Among them, the die coating method, which is excellent in uniform coating property, is preferable. Further, in order to prevent foreign matter from entering, it is preferable to carry out the coating step in an environment such as a clean room where few foreign matter is generated.

The photosensitive resin composition layer of the photosensitive film with a support of the present invention exhibits the property of excellent flexibility. Even if the photosensitive resin composition layer is cut out with a cutter knife, it is preferable that scattering or cracks of the photosensitive resin composition are not found. Further, even if the photosensitive resin composition layer is bent by 180°, It is preferable that no scattering or cracks of the product can be seen. The flexibility can be measured according to the description of <Evaluation of appearance and flexibility of film> described later.

[Printed wiring board]
The printed wiring board of the present invention includes 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 manufactured using the above-mentioned photosensitive film or the photosensitive film with a support. Hereinafter, a case where the insulating layer is a solder resist will be described.

<Coating and drying process>
The photosensitive resin composition is directly applied in a resin varnish state onto the circuit board, and the organic solvent is dried to form a photosensitive film on the circuit board.

Examples of the circuit board include a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, and a thermosetting polyphenylene ether board. Here, the circuit board means a board on which a patterned conductor layer (circuit) is 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 outermost layers of the multilayer printed wiring board are patterned conductor layers (circuits) is also used. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening treatment, copper etching or the like.

As the coating method, the whole surface printing by the screen printing method is generally used in many cases, but any means may be used as long as it is a coating method capable of uniformly coating. 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 , Brush coating, and other usual coating methods can all be used. After coating, if necessary, it is dried in a hot air oven or a far infrared oven. The drying condition is preferably 80° C. to 120° C. for 3 minutes to 13 minutes. In this way, the photosensitive film is formed on the circuit board.

<Laminating process>
When a photosensitive film with a support is used, the photosensitive resin composition layer side is laminated on one side or both sides of the circuit board using a vacuum laminator. In the laminating step, when the photosensitive film with a support has a protective film, the protective film is removed, and then the photosensitive film with a support and the circuit board are preheated if necessary to prepare a photosensitive resin composition. The physical layer is pressed onto the circuit board while being pressed and heated. For the photosensitive film with a support, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used.

The conditions of the laminating step are not particularly limited, but for example, the pressure bonding temperature (lamination 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 ), pressure bonding time is preferably 5 seconds to 300 seconds, and air pressure is 20 mmHg (26.7 hPa) or less. Is preferred. Further, the laminating step may be a batch type or a continuous type using a roll. The vacuum laminating method can be performed using a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include, for example, vacuum applicator manufactured by Nikko Materials Co., vacuum pressure type laminator manufactured by Meiki Co., Ltd., roll type dry coater manufactured by Hitachi Industries Co., Ltd., vacuum laminator manufactured by Hitachi AIC Co., Ltd., etc. be able to. In this way, the 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 laminating process, then, a predetermined portion of the photosensitive resin composition layer is irradiated with an actinic ray through a mask pattern to make the photosensitive portion of the irradiated portion photosensitive. An exposure step of photocuring the resin composition layer is performed. Examples of the actinic rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. Dose of ultraviolet light is approximately ^{10mJ / cm 2 ~1000mJ / cm 2} . As the exposure method, there are 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 parallel rays are used for exposure without making close contact, but either may be used. Further, when a support is present on the photosensitive resin composition layer, it may be exposed from the support or may be exposed after peeling the support.

The solder resist is excellent in resolution because it uses the photosensitive resin composition of the present invention. Therefore, as the exposure pattern in the mask pattern, for example, the ratio (L/S) of the circuit width (line; L) and the width between the circuits (space; S) is 100 μm/100 μm or less (that is, the wiring pitch is 200 μm or less). , 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) can be used Is. Note that the pitch does not have to be the same over the entire circuit board.

<Developing process>
After the exposure process, if a support is present on the photosensitive resin composition layer, the support is removed, and then the non-photocured part (unexposed part) is removed by wet development or dry development. Then, a pattern can be formed by developing.

In the case of the above-mentioned wet development, a developing solution which is safe and stable and has good operability, such as an alkaline aqueous solution, an aqueous developing solution or an organic solvent, is used as the developing solution. Among them, the developing step using an alkaline aqueous solution is preferable. Further, as a developing method, a known method such as spraying, rocking dipping, brushing, scraping, etc. is appropriately adopted.

Examples of the alkaline aqueous solution used as the developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate, sodium phosphate. , An alkali metal phosphate such as potassium phosphate, sodium pyrophosphate, an aqueous solution of an alkali metal pyrophosphate such as potassium pyrophosphate, and an aqueous solution of an organic base containing no metal ion such as tetraalkylammonium hydroxide, An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferable because it does not contain metal ions and does not affect the semiconductor chip.
To these alkaline aqueous solutions, a surfactant, a defoaming agent or the like can be added to the developing solution in order to improve the developing effect. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8 to 12, and more preferably in the range of 9 to 11. The base concentration of the alkaline aqueous solution is preferably 0.1% by mass to 10% by mass. The temperature of the alkaline aqueous solution can be appropriately selected depending on the developability of the photosensitive resin composition layer, but is preferably 20°C to 50°C.

Examples of the organic solvent used as a developer include 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, 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 developing solution. Further, the temperature of such an organic solvent can be adjusted according to the developability. Further, such organic solvents can be used alone or in combination of two or more kinds. Examples of the organic solvent-based developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone and γ-butyrolactone.

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

<Thermosetting (post-baking) process>
After the development process is completed, a thermosetting (post-baking) process is performed to form a solder resist. Examples of the post-baking process include an ultraviolet irradiation process using a high pressure mercury lamp and a heating process using a clean oven. In the case of irradiating with ultraviolet rays, the irradiation amount can be adjusted as necessary, and for example, the irradiation amount can be about 0.05 J/cm ^{2 to} 10 J/cm ² . The heating conditions may be appropriately selected depending on the type and content of the resin component in the photosensitive resin composition, but are preferably in the range of 150°C to 220°C for 20 minutes to 180 minutes, more preferably It is selected in the range of 160 to 200° C. for 30 to 120 minutes.

<Other processes>
The printed wiring board may further include a drilling step and a desmearing step after forming the solder resist. These steps may be performed according to various methods known to those skilled in the art used for manufacturing printed wiring boards.

After forming the solder resist, a via hole and a through hole are formed by performing a drilling process on the solder resist formed on the circuit board, if desired. The drilling step can be carried out, for example, by a known method such as a drill, a laser, plasma or the like, and if necessary, a combination of these methods can be carried out, but a drilling step by a laser such as a carbon dioxide laser or a YAG laser is preferable.

The desmear process is a process of performing a desmear process. A resin residue (smear) is generally attached to the inside of the opening formed in the drilling process. Since such smear causes defective electrical connection, a process (desmear process) for removing smear is performed in this step.

The desmear treatment may be performed by a dry desmear treatment, a wet desmear treatment, or a combination thereof.

Examples of the dry desmear treatment include a desmear treatment using plasma. The desmear processing using plasma can be implemented using a commercially available plasma desmear processing apparatus. Among commercially available plasma desmear processing devices, examples suitable for manufacturing printed wiring boards include microwave plasma devices manufactured by Nissin and atmospheric pressure plasma etching devices manufactured by Sekisui Chemical Co., Ltd.

Examples of the wet desmear treatment include a desmear treatment using an oxidant solution. When the desmear treatment is performed using the oxidizing agent solution, it is preferable to perform the swelling treatment with the swelling solution, the oxidizing treatment with the oxidizing agent solution and the neutralizing treatment with the neutralizing solution in this order. Examples of the swelling liquid include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing the substrate having the via holes and the like in a swelling liquid heated to 60° C. to 80° C. for 5 minutes to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganate aqueous solution, and examples thereof include a solution of potassium permanganate or sodium permanganate dissolved in an aqueous solution of sodium hydroxide. The oxidation treatment with the oxidizing agent solution is preferably performed by immersing the substrate after the swelling treatment in the oxidizing agent solution heated to 60° C. to 80° C. for 10 minutes to 30 minutes. Examples of commercially available alkaline permanganate aqueous solutions include "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotech Japan. The neutralization treatment with the neutralization liquid is preferably performed by immersing the substrate after the oxidation treatment in the neutralization liquid at 30°C to 50°C for 3 minutes to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan.

When the dry desmear treatment and the wet desmear treatment are performed in combination, the dry desmear treatment may be performed first or the wet desmear treatment may be performed first.

When the insulating layer is used as the interlayer insulating layer, it can be performed in the same manner as in the case of the solder resist, and the hole forming step, the desmear step, and the plating step may be performed after the thermosetting step.

The plating step is a step of forming a conductor layer on the insulating layer. The conductor layer may be formed by a combination of electroless plating and electroplating, or 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 forming the pattern thereafter, for example, a subtractive method, a semi-additive method or the like known to those skilled in the art can be used.

[Semiconductor device]
The semiconductor device of the present invention includes a printed wiring board. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

Examples of the semiconductor device include various semiconductor devices used for electric products (for example, computers, mobile phones, digital cameras and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships and aircrafts).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conducting portion" is a "portion for transmitting an electric signal in the printed wiring board", and the location may be a surface or an embedded portion. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively. Specifically, the wire bonding mounting method, the flip chip mounting method, and the bumpless method are used. Examples thereof include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, the "mounting method using a bump-free build-up layer (BBUL)" is a "mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board to connect the semiconductor chip and wiring on the printed wiring board". Is.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the following description, “parts” and “%” representing amounts mean “parts by mass” and “mass %”, respectively, unless otherwise specified.

(Preparation of inorganic filler)
Inorganic fillers 1 to 5 are "Admafine" manufactured by Admatechs, "SFP series" manufactured by Denki Kagaku Kogyo, "SP(H) series" manufactured by Nippon Steel & Sumikin Materials Co., Ltd., "Sciqas series" manufactured by Sakai Chemical Co., Ltd. , "Cyphostar Series" manufactured by Nippon Shokubai Co., Ltd., alone or in combination, subjected to surface treatment with an aminosilane coupling agent (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) and classified.
The inorganic filler 6 was obtained by performing the same surface treatment as the inorganic fillers 1 to 5 using alumina (“AZ series” and “AX series” manufactured by Nippon Steel & Sumikin Materials Co., Ltd.) and classifying. ..
The inorganic filler 7 was obtained by subjecting barium sulfate (“B series” and “BF series” manufactured by Sakai Chemical Industry Co., Ltd.) to the same surface treatment as the inorganic fillers 1 to 5 and classification. ..
The particle size distribution and specific surface area of the inorganic fillers 1 to 7 were measured by the following methods.

50 mg of the powder of the inorganic filler 1, 2 g of nonionic dispersant (“T208.5” manufactured by NOF CORPORATION), and 40 g of pure water were weighed in a vial and dispersed by ultrasonic waves for 20 minutes. The particle size distribution was measured by a batch cell method using a laser diffraction type particle size distribution analyzer (LA-950, manufactured by Horiba, Ltd.), and the average particle size, D ₉₀ was calculated. The average particle size was similarly calculated 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 similarly measured for the inorganic fillers 2 to 7.
The results of the average particle size and the specific surface area of each inorganic filler were as follows.
Inorganic filler 1: average particle size 0.80 μm, D ₉₀ 2.2 μm, specific surface area 4.1 m ² /g
Inorganic filler 2: average particle size 1.75 μm, D ₉₀ 4.2 μm, specific surface area 2.2 m ² /g
Inorganic filler 3: average particle size 0.50 μm, D ₉₀ 1.3 μm, specific surface area 6.3 m ² /g
Inorganic filler 4: average particle size 2.10 μm, D ₉₀ 4.7 μm, specific surface area 1.0 m ² /g
Inorganic filler 5: average particle size 0.20 μm, D ₉₀ 0.5 μm, specific surface area 12.0 m ² /g
Inorganic filler 6: average particle size 0.80 μm, D ₉₀ 2.4 μm, specific surface area 4.0 m ² /g
Inorganic filler 7: average particle size 0.80 μm, D ₉₀ 2.8 μm, specific surface area 5.0 m ² /g

(Synthesis Example 1: Synthesis of component A-1)
162 parts of 1,1′-bis(2,7-diglycidyloxynaphthyl)methane (“EXA-4700”, manufactured by Dainippon Ink and Chemicals, Inc.) having an epoxy equivalent of 162, a gas introduction pipe, a stirring device, and a cooling pipe. Then, 340 parts of carbitol acetate was added to a flask equipped with a thermometer and dissolved by heating, and 0.46 part of hydroquinone and 1 part of triphenylphosphine were added. This mixture was heated to 95 to 105° C., 72 parts of acrylic acid was gradually added dropwise, and the mixture was reacted for 16 hours. The reaction product was cooled to 80 to 90° C., 80 parts of tetrahydrophthalic anhydride was added, reacted for 8 hours, and cooled. Thus, 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, Comparative Examples 1 to 4>
The components were blended in the blending ratios shown in the table below, and a resin varnish was prepared using a high-speed rotary mixer. Next, a PET film (manufactured by Toray Industries, Inc., "Lumirror T6AM", thickness 38 μm, softening point 130° C., “releasing”, which was mold-release treated with an alkyd resin-based mold release agent (“AL-5” manufactured by Lintec Co., Ltd.) as a support. Mold PET”) was prepared. The prepared resin varnish was evenly applied to such a release PET by a die coater so that the thickness of the photosensitive resin composition layer after drying would be 40 μm, and dried at 80° C. to 110° C. for 6 minutes to release the resin varnish. A support-attached photosensitive film having a photosensitive resin composition layer on a mold PET was obtained.

The measurement method and evaluation method in the physical property evaluation will be described.

<Evaluation of film appearance and flexibility>
The appearance of the photosensitive resin composition layer of the photosensitive film with a support prepared in Examples and Comparative Examples was visually observed. Further, the scattering of resin and the occurrence of cracks when the photosensitive resin composition layer was cut out with a cutter knife were visually observed. Furthermore, the generation of cracks when the photosensitive film with a support was bent by 180° was visually observed and evaluated according to the following criteria.
◯: There is no cissing or unevenness, and no scattering or cracking of resin can be seen.
Poor: Repelling, unevenness, resin scattering, or cracks are found.

<Measurement of average linear thermal expansion coefficient>
(Formation of cured product for evaluation)
The photosensitive resin composition layers of the photosensitive films with a support obtained in Examples and Comparative Examples were exposed to 100 mJ/cm ² of ultraviolet rays and photocured. After that, a 1% by mass sodium carbonate aqueous solution at 30° C. as a developer was spray-developed for 2 minutes on the entire surface of the photosensitive resin composition layer at a spray pressure of 0.2 MPa. After spray development, irradiation with 1 J/cm ² of ultraviolet rays was performed, and heat treatment was further performed at 190° C. for 90 minutes to obtain a cured product. Then, the support was peeled off to obtain a cured product for evaluation.

(Measurement of average linear thermal expansion coefficient)
The cured product for evaluation was cut into a test piece having a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer (Thermo Plus, TMA8310 manufactured by Rigaku Corporation). After mounting the test piece on the above-mentioned apparatus, the load was 1 g and the temperature rising rate was 5 times/minute. The average linear thermal expansion coefficient (ppm) from 25° C. to 150° C. in the second measurement was calculated.

<Evaluation of resolution and crack resistance>
(Formation of evaluation laminate)
The copper layer of the glass epoxy substrate (copper-clad laminate) on which the circuit in which the copper layer having a thickness of 18 μm is patterned is roughened by a treatment with a surface treatment agent (CZ8100, manufactured by Mec Co.) containing an organic acid. Was applied. Next, the photosensitive resin composition layer of the photosensitive film with a support obtained in each of Examples and Comparative Examples was arranged so as to be in contact with the copper circuit surface, and a vacuum laminator (VP160, manufactured by Nikko Materials Co., Ltd.) was used. By laminating, the copper clad laminate, the photosensitive resin composition layer, and the support were laminated in this order to form a laminate. The pressure bonding conditions were a vacuuming time of 30 seconds, a pressure bonding temperature of 80° C., a pressure bonding pressure of 0.7 MPa, and a pressure time of 30 seconds. The laminate was allowed to stand at room temperature for 30 minutes or longer, and exposed to ultraviolet rays from above the support of the laminate using a pattern forming device using a round hole pattern. The exposure pattern has openings: 50 μm/60 μm/70 μm/80 μm/90 μm/100 μm round holes, L/S (line/space): 50 μm/50 μm, 60 μm/60 μm, 70 μm/70 μm, 80 μm/80 μm, 90 μm/90 μm, 100 μm A quartz glass mask that draws a line and space of /100 μm was used. After standing at room temperature for 30 minutes, the support was peeled off from the laminate. A 1 mass% sodium carbonate aqueous solution at 30° C. as a developer was spray-developed for 2 minutes at a spray pressure of 0.2 MPa on the entire surface of the photosensitive resin composition layer on the laminated plate. After spray development, irradiation with 1 J/cm ² of ultraviolet rays was performed, and heat treatment was further performed at 180° C. for 30 minutes to cure the photosensitive resin composition layer, and an insulating layer having openings was formed on the laminate. .. This was used as an evaluation laminate.

(Evaluation of resolution)
The round hole formed by patterning with respect to the evaluation laminated body was observed by SEM (magnification: 1000 times), and the minimum via diameter without residue and the minimum L/S without filling or peeling were measured. When there was no minimum L/S with no resin embedding or peeling, "x" was given. The L/S shape was evaluated according to the following criteria.
◯: Three points of L/S were observed and there was no peeling or filling between all L/S.
X: Three points of L/S were observed, and resin embedding or peeling was observed between any of the L/S.

(Crack resistance evaluation)
The laminated body for evaluation was exposed to the atmosphere of −65° C. for 15 minutes, heated at a heating rate of 180° C./minute, and then exposed to the atmosphere of 150° C. for 15 minutes, and then 180° C./minute. A test was repeated 500 times, in which the heat cycle treatment of lowering the temperature was performed. After the test, the degree of cracking and peeling of the evaluation substrate was observed with an optical microscope ("ECLIPSE LV100ND" manufactured by Nikon Corporation), and evaluated according to the following criteria.
◯: No crack or peeling observed.
X: Cracks and peeling are recognized.

Abbreviations in the table are as follows.
Component (A)-ZAR-2000: Bisphenol A type epoxy acrylate (manufactured by Nippon Kayaku Co., acid value 99 mgKOH/g, solid content concentration about 70%).
-A-1: A-1 component synthesized in Synthesis Example 1 (nonvolatile content 70%)
Component (B)/inorganic filler 1: silica, average particle size 0.80 μm, D ₉₀ 2.2 μm, specific surface area 4.1 m ² /g
Inorganic filler 2: silica, average particle size 1.75 μm, D ₉₀ 4.2 μm, specific surface area 2.2 m ² /g
Inorganic filler 3: silica, average particle size 0.50 μm, D ₉₀ 1.3 μm, specific surface area 6.3 m ² /g
Inorganic filler 4: silica, average particle size 2.10 μm, D ₉₀ 4.7 μm, specific surface area 1.0 m ² /g
Inorganic filler 5: silica, average particle size 0.20 μm, D ₉₀ 0.5 μm, specific surface area 12.0 m ² /g
Inorganic filler 6: Alumina, average particle size 0.80 μm, D ₉₀ 2.4 μm, specific surface area 4.0 m ² /g
Inorganic filler 7: barium sulfate, average particle size 0.80 μm, D ₉₀ 2.8 μm, specific surface area 5.0 m ² /g
Component (C) Irgacure 819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by BASF)
Component (D)-NC3000H: Biphenyl type epoxy resin (Nippon Kayaku Co., epoxy equivalent 272)
1031S: Tetrakishydroxyphenylethane type epoxy resin (Mitsubishi Chemical Co., epoxy equivalent 200)
(E) component-DPHA: dipentaerythritol hexaacrylate (Nippon Kayaku Co., acrylic equivalent about 96)
Component (F)-EDGAc: Ethyl diglycol acetate-MEK: Methyl ethyl ketone-Content of component (B): Content of component (B) when the total solid content of the photosensitive resin composition is 100% by mass.

From the results in the above table, it was found that the examples using the photosensitive resin composition of the present invention had the appearance, flexibility, resolution and crack resistance of the film, and had a low average linear thermal expansion coefficient.

On the other hand, Comparative Example 1 in which the content of the inorganic filler exceeded 85% by mass was inferior in the appearance, flexibility and resolution of the film and could not be used as a photosensitive resin composition. Comparative Example 2 in which the content of the inorganic filler is less than 60% by mass has a high average coefficient of linear thermal expansion. Further, the crack resistance was poor, and it could not be used as a photosensitive resin composition. Comparative Example 3 using an inorganic filler having an average particle size of less than 0.5 μm and a specific surface area of more than 10 m ² /g has a high average coefficient of linear thermal expansion because the component (B) cannot be sufficiently filled. .. Further, the film had poor appearance, flexibility, resolution and crack resistance, and could not be used as a photosensitive resin composition. Comparative Example 4, which uses an inorganic filler having a specific surface area of less than 1.4 m ² /g, has a poor minimum resolution and thus has a minimum via diameter of more than 100 μm, and therefore cannot be used as a photosensitive resin composition. There wasn't.

In each of the examples, it was confirmed that even when the components (E) to (F) and the like were not contained, the same results as those of the above-mentioned examples were obtained although there were some differences.

Claims (11)

(A) a resin containing an ethylenically unsaturated group and a carboxyl group,
(B) An inorganic filler having an average particle size 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,
A photosensitive resin composition containing (C) a photopolymerization initiator and (D) an epoxy resin,
The component (A) has a naphthalene skeleton,
The content of component (B), when the total solid content of the photosensitive resin composition is 100 mass% state, and are 60 wt% or more and 85 mass% or less,
The average particle size of the component (B) is a particle size at which the cumulative frequency of the volume-based particle size distribution obtained by measurement with a laser diffraction/scattering particle size distribution measuring device is 50%,
(B) a specific surface area of the component, Ru specific surface der obtained by measurement by the BET fully automatic specific surface area measuring apparatus, a photosensitive resin composition. The average linear thermal expansion coefficient at 25° C. to 150° C. of the cured product obtained by photo-curing the photosensitive resin composition at 190° C. for 90 minutes is 10 ppm or more and 45 ppm or less. Photosensitive resin composition. (A) component is an acid-modified naphthalene skeleton-containing epoxy (meth) acrylate, photosensitive resin composition according to claim 1 or 2. Component (D) comprises at least one of biphenyl epoxy resin and tetraphenyl ethane epoxy resin, photosensitive resin composition according to any one of claims 1-3. (B) a specific surface area of the component is less than or equal to ^2m 2 / g or more ^7m 2 / g, the photosensitive resin composition according to any one of claims 1-4. (B) component comprises silica, the photosensitive resin composition according to any one of claims 1-5. Containing photosensitive resin composition according to any one of claims 1 to 6 photosensitive film. A support, provided on the support, the support with a photosensitive film having a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1-6. Printed circuit board containing the formed insulating layer with a cured product of the photosensitive resin composition according to any one of claims 1-6. The printed wiring board according to claim 9 , wherein the insulating layer is a solder resist. To claim 9 or 1 0 includes a printed wiring board according semiconductor device.