JP2022119819A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having excellent resolution which can form a cured product having a low average linear thermal expansion coefficient and forms a film excellent in appearance, flexibility and crack resistance when formed into a film shape.

SOLUTION: There is provided a photosensitive resin composition which comprises (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an 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 m²/g or more and 10 m²/g or less, (C) a photopolymerization initiator and (D) an epoxy resin, wherein the content of (B) component is 60 mass% or more and 85 mass% or less, when the total slid content of the photosensitive resin composition is defined as 100 mass%.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

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

A printed wiring board is sometimes provided with a solder resist as a permanent protective film to prevent solder from adhering to areas where solder is not required and to prevent corrosion of the circuit board. As a solder resist, for example, a photosensitive resin composition as described in Patent Document 1 is generally used.

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 ultra-accelerated high temperature between fine wirings. HAST resistance to high humidity life test (HAST) is required. In recent years, with the increasing density of printed wiring boards, solder resists are also required to have higher performance. In particular, the demand for crack resistance is increasing year by year, and it is important to provide further durability.

In order to increase the crack resistance, for example, a method of filling the photosensitive resin composition with a high amount of inorganic filler is conceivable. There is a possibility that the sensitivity of the bottom will deteriorate and undercut will occur, or that the aperture will not be sufficiently open due to light halation.

Moreover, from the viewpoint of productivity, solder resists are required to be less likely to crack during handling, and less likely to cause cracks and resin scattering when the solder resist is cut.

An object of the present invention is to provide a cured product having excellent crack resistance and a low average coefficient of linear thermal expansion, and a photosensitive resin composition having excellent appearance, flexibility, and resolution when formed into a film. Object: 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 by the present inventors to solve the above problems, the inclusion of an inorganic filler having a predetermined average particle size and a predetermined specific surface area in a photosensitive resin composition improves resolution, crack resistance, Also, the inventors have found that the appearance and flexibility of the film are improved when formed into a film shape, 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;
(C) a photopolymerization initiator, and (D) a photosensitive resin composition containing an epoxy resin,
A photosensitive resin composition in which the content of 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] After photocuring the photosensitive resin composition, the average linear thermal expansion coefficient at 25 ° C. to 150 ° C. of the cured product obtained by heat curing at 190 ° C. for 90 minutes is 10 ppm or more and 45 ppm or less. The photosensitive resin composition according to .
[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 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 one of a biphenyl-type epoxy resin and a tetraphenylethane-type epoxy resin.
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the component (B) has a specific surface area of 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, comprising a support and a photosensitive resin composition layer containing the photosensitive resin composition according to any one of [1] to [7] provided on the support. sex film.
[10] A printed wiring board comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of [1] to [7].
[11] The printed wiring board of [10], wherein the insulating layer is a solder resist.
[12] A semiconductor device comprising 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 that is excellent in appearance, flexibility, and resolution when molded into a film. Product: 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.

The photosensitive resin composition, photosensitive film, photosensitive film with support, printed wiring board, and semiconductor device of the present invention are described in detail below.

[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. ² /g or more and 10 m ² /g or less of an inorganic filler, (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, it is 60% by mass or more and 85% by mass or less.

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

<(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.

Ethylenically unsaturated groups include, for example, vinyl groups, allyl groups, propargyl groups, butenyl groups, ethynyl groups, phenylethynyl groups, maleimide groups, nadimide groups, and (meth)acrylic groups. from the viewpoint of (meth) acrylic group is preferred. A "(meth)acryl group" refers to a methacryl group and an acryl group.

Component (A) is not particularly limited as long as it is a compound that has an ethylenically unsaturated group and a carboxyl group and enables photoradical polymerization and alkali development. Resins that also have one or more ethylenically unsaturated groups are preferred.

One aspect of the resin containing an ethylenically unsaturated group and a carboxyl group includes an acid-modified unsaturated epoxy ester resin obtained by reacting an epoxy compound with an unsaturated carboxylic acid and further with an acid anhydride. Specifically, an unsaturated epoxy ester resin is obtained by reacting an epoxy compound with an unsaturated carboxylic acid, and an acid-modified unsaturated epoxy ester resin can be obtained by 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, modified bisphenol F-type epoxy resin obtained by reacting epichlorohydrin with bisphenol F-type epoxy resin to modify it to be trifunctional or higher; bisphenol-type epoxy resin; biphenol-type epoxy resin, tetramethylbiphenol type Novolac epoxy resins such as phenol novolak epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, alkylphenol novolac epoxy resin; bisphenol AF epoxy resin, and perfluoroalkyl epoxy Fluorine-containing epoxy resins such as resins; 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 novolak-type epoxy resin, poly Epoxy resins having a naphthalene skeleton (naphthalene skeleton-containing epoxy resins) such as naphthalene-type epoxy resins obtained by the condensation reaction of hydroxynaphthalene and aldehydes; bixylenol-type epoxy resins; dicyclopentadiene-type epoxy resins; trisphenol-type epoxy resins tert-butyl-catechol type epoxy resin; epoxy resin containing condensed ring skeleton such as anthracene type epoxy resin; glycidylamine type epoxy resin; glycidyl ester type epoxy resin; biphenyl type epoxy resin; linear aliphatic epoxy resin; butadiene heterocyclic epoxy resin; spiro ring-containing epoxy resin; cyclohexanedimethanol-type epoxy resin; trimethylol-type epoxy resin; tetraphenylethane-type epoxy resin; polyglycidyl (meth)acrylate , glycidyl group-containing acrylic resins such as copolymers of glycidyl methacrylate and acrylic acid ester; fluorene-type epoxy resins; halogenated epoxy resins, and the like.

An epoxy resin containing an aromatic skeleton is preferable from the viewpoint of reducing the average linear thermal expansion coefficient. Here, the aromatic skeleton is a concept including polycyclic aromatics and aromatic heterocycles. Among them, a naphthalene skeleton-containing epoxy resin, a condensed ring skeleton-containing epoxy resin, a biphenyl type epoxy resin, a bisphenol F type epoxy resin, a bisphenol A type epoxy resin, a cresol novolak type epoxy resin, and a glycidyl ester type epoxy resin are preferable. Among them, since the rigidity of the molecule increases, the movement of the molecule is suppressed, and as a result, the glass transition temperature of the cured product of the resin composition increases, and the average linear thermal expansion coefficient of the cured product decreases. A skeleton-containing epoxy resin, an epoxy resin containing a condensed ring skeleton, and a biphenyl-type epoxy resin are more preferred, and a naphthalene skeleton-containing epoxy resin is even more preferred. As the naphthalene skeleton-containing epoxy resin, a dihydroxynaphthalene-type epoxy resin, a polyhydroxybinaphthalene-type epoxy resin, and a naphthalene-type epoxy resin obtained by a condensation reaction of polyhydroxynaphthalene and an aldehyde are preferable.

Dihydroxynaphthalene type epoxy resins include, for example, 1,3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, 1,6-diglycidyloxynaphthalene, 2,3-di glycidyloxynaphthalene, 2,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene and the like.

Examples of polyhydroxy binaphthalene type epoxy resins 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.

Examples of naphthalene-type epoxy resins 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, polyhydroxybinaphthalene-type epoxy resins having two or more naphthalene skeletons in one molecule and naphthalene-type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes are preferred, and in particular epoxy 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 have It is preferable in terms of excellent heat resistance.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, cinnamic acid and crotonic acid, and 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 this specification, the epoxy ester resin that is the reaction product of the above epoxy compound and (meth)acrylic acid may be referred to as "epoxy (meth)acrylate", where the epoxy group of the epoxy compound is It is substantially extinguished by the reaction with (meth)acrylic acid. "(Meth)acrylate" refers to methacrylate and acrylate. Acrylic acid and methacrylic acid are sometimes collectively referred to as "(meth)acrylic acid".

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

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 too. Moreover, you may use a solvent and a polymerization inhibitor as needed.

Acid-modified epoxy (meth)acrylate is preferred as the acid-modified unsaturated epoxy ester resin. The “epoxy” in the acid-modified unsaturated epoxy ester resin represents a structure derived from the epoxy compound described above. For example, "acid-modified bisphenol-type epoxy (meth)acrylate" is an acid-modified unsaturated epoxy ester resin obtained by using a bisphenol-type epoxy resin as an epoxy compound and using (meth)acrylic acid as an unsaturated carboxylic acid. point to The preferred range of acid-modified epoxy (meth)acrylates is derived from the preferred range of epoxy compounds. 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 coefficient of linear thermal expansion. Acid-modified naphthalene skeleton-containing epoxy (meth)acrylate is a compound obtained by reacting a reaction product of naphthalene-type epoxy resin and (meth)acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. .

Such an acid-modified unsaturated epoxy ester resin can be a commercially available product, and a specific example is "ZAR-2000" manufactured by Nippon Kayaku Co., Ltd. reaction product), “ZFR-1491H”, “ZFR-1533H” (bisphenol F type epoxy resin, acrylic acid, and tetrahydrophthalic anhydride reaction product), Showa Denko “PR-300CP” (cresol novolac type epoxy reaction product of resin, acrylic acid, and acid anhydride), and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Another embodiment of the resin containing an ethylenically unsaturated group and a carboxyl group is a (meth)acrylic resin having a structural unit obtained by polymerizing (meth)acrylic acid, and an ethylenically unsaturated group-containing epoxy compound. Unsaturated modified (meth)acrylic resins into which ethylenically unsaturated groups are introduced by reaction are mentioned. Ethylenically unsaturated group-containing epoxy compounds include, for example, glycidyl methacrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate and the like. Furthermore, it is also possible to react an acid anhydride with the hydroxyl group generated during the introduction of the unsaturated group. As the acid anhydride, the same acid anhydride as described above can be used, and the preferred range is also the same.

Commercial products can be used as such unsaturated modified (meth)acrylic resins. Specific examples include "SPC-1000" and "SPC-3000" manufactured by Showa Denko KK, and "Cychromer" manufactured by Daicel Allnex. P (ACA) Z-250", "Cychromer P (ACA) Z-251", "Cychromer P (ACA) Z-254", "Cychromer P (ACA) Z-300", "Cychromer P ( ACA) Z-320” and the like.

The weight average molecular weight of component (A) is preferably 1000 or more, more preferably 1500 or more, and even more preferably 2000 or more, from the viewpoint of film-forming properties. From the viewpoint of developability, the upper limit is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7,500 or less. A weight average molecular weight is a weight average molecular weight of polystyrene conversion measured by 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, from the viewpoint of improving the alkali developability of the photosensitive resin composition. is more preferred, and 1 mgKOH/g or more is even more preferred. 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 elution of the fine pattern of the cured product by development and improving insulation reliability. It is preferably 100 mgKOH/g or less, and more preferably 100 mgKOH/g or less. Here, the acid value is the residual acid value of the carboxyl groups present in the component (A), and the acid value can be measured by the following method. First, about 1 g of the resin solution to be measured is accurately 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 as 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 x Vf x 56.1/(Wp x I)

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

In the production of 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 the total carboxyl groups of the unsaturated carboxylic acid and the acid anhydride is 1. : It is preferably in the range of 0.8 to 1.3, more preferably in the range of 1:0.9 to 1.2.

From the viewpoint of improving alkali developability, the content of component (A) is preferably 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. It is more preferable to set the content to 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 even more 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 give a cured product having a low average coefficient of linear thermal expansion.

The material of the inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and 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 zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica, alumina and barium sulfate are preferred, and silica is particularly preferred. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

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

The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction/scattering particle size distribution measuring device, and the particle size at which the cumulative frequency becomes 50% (d50) is measured as the average particle size. be able to. As the measurement sample, one obtained by ultrasonically dispersing an inorganic filler in water can be preferably used. As the laser diffraction scattering type particle size distribution analyzer, Horiba's "LA-500", Shimadzu Corporation's "SALD-2200" and the like can be used.

The particle size (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 linear thermal expansion coefficient. , and more preferably 1 μm or more. The upper limit of _D90 is 5.5 μm or less, preferably 5 μm or less, more preferably 4.5 μm or less, from the viewpoint of obtaining excellent resolution. D90 can be measured in the same manner as average particle size.

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

From the viewpoint of obtaining excellent resolution, the specific surface area of the inorganic filler is 1.4 m ² /g or more, preferably 1.7 m ² /g or more, more preferably 2 m ² /g or more. 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. 5 m ² /g or less.

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

Inorganic fillers include aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilane compounds, organosilazane compounds, titanates, from the viewpoint of improving moisture resistance and dispersibility. It is preferably treated with one or more surface treatment agents 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 Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "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 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 more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of suppressing the melt viscosity of the resin varnish and the melt viscosity in the sheet form, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and further preferably 0.5 mg/m ² or less. preferable.

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (eg, 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, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

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

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

Component (C) is not particularly limited, but examples include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl ) methyl]-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and other α-aminoalkylphenones Photopolymerization initiator; oxime ester 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)phenylphosphinate, 4,4′-bis(diethylamino)benzophenone, 1-hydroxy-cyclohexyl-phenylketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1 -[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and the like. Also, a sulfonium salt-based photopolymerization initiator and the like can be used. Any one of these may be used alone, or two or more thereof may be used in combination.

Further, the photosensitive resin composition contains, in combination with the component (C), 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 contain photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, thioxanthones, and the like. good. Any one of these may be used alone, or two or more thereof may be used in combination.

Specific examples of the component (C) include "Omnirad907", "Omnirad369", "Omnirad379", "Omnirad819", and "OmniradTPO" manufactured by IGM, "IrgacureOXE-01" and "IrgacureOXE-02" manufactured by BASF, and "N-1919" manufactured by ADEKA.

From the viewpoint of sufficiently photocuring the photosensitive resin composition and improving the insulation reliability, the content of the component (C) is preferably It is 0.01% by mass or more, more preferably 0.03% by mass or more, and still more 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 even more preferably 0.3% by mass or less, from the viewpoint of suppressing deterioration in resolution due to excessive sensitivity.

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

Examples of component (D) include fluorine-containing epoxy resins such as bisphenol AF type epoxy resins and perfluoroalkyl type epoxy resins; bisphenol A type epoxy resins; bisphenol F type epoxy resins; bisphenol S type epoxy resins; Epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin; naphthol novolak type epoxy resin; phenol novolak type epoxy resin; tert-butyl-catechol type epoxy resin; naphthalene type epoxy resin; naphthol type epoxy resin; anthracene type epoxy Resin; Glycidylamine type epoxy resin; Glycidyl ester type epoxy resin; Cresol novolac type epoxy resin; Biphenyl type epoxy resin; Linear aliphatic epoxy resin; cyclic epoxy resin; heterocyclic epoxy resin; spiro ring-containing epoxy resin; cyclohexane dimethanol type epoxy resin; naphthylene ether type epoxy resin; trimethylol type epoxy resin; Bisphenol F-type epoxy resins and biphenyl-type epoxy resins are preferred, and biphenyl-type epoxy resins are more preferred, from the viewpoint of improving adhesion. From the viewpoint of improving heat resistance, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, naphthylene ether-type epoxy resins, and tetraphenylethane-type epoxy resins are preferable, and tetraphenylethane-type epoxy resins are more preferable. . An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. From the viewpoint of improving adhesion and heat resistance, 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 non-volatile component of the epoxy resin is 100 mass %, at least 50 mass % or more of the epoxy resin preferably has two or more epoxy groups in one molecule. As component (E), two or more epoxy resins may be used in combination.

Specific examples of epoxy resins include "HP4032", "HP4032D", "HP4032SS", and "HP4032H" (naphthalene type epoxy resins) manufactured by DIC Corporation, "828US" and "jER828EL" (bisphenol A type epoxy resins) 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. (mixture 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" manufactured by Nagase ChemteX Corporation (glycidyl ester type epoxy resin), Daicel's "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure), Nippon Steel & Sumikin Chemical Co., Ltd. "ZX1658", " ZX1658GS" (liquid 1,4-glycidylcyclohexane), Mitsubishi Chemical's "630LSD" (glycidylamine type epoxy resin), Daikin Industries Ltd.'s "E-7432", "E-7632" (perfluoroalkyl type epoxy resin), DIC's "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolak 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" (naphthylene ether type epoxy resin), Nippon Kayaku "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin) , "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" and "CG-500" manufactured by Osaka Gas Chemicals, Mitsubishi Chemical "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "1031S" (tetraphenylethane type epoxy resin), "YL7760" (bisphenol AF type epoxy resin) and the like.

The content of 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, and still more preferably 8% by mass or more. The upper limit of the epoxy resin content is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

The epoxy equivalent of the epoxy resin is preferably 50-5000, more preferably 50-3000, even more preferably 80-2000, still more preferably 110-1000. Within this range, the crosslink density of the cured product of the photosensitive resin composition is sufficient, and an insulating layer with a small surface roughness can be obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing one equivalent of epoxy groups.

The weight average molecular weight of the epoxy resin is preferably 100-5000, more preferably 250-3000, still more preferably 400-1500. Here, the weight average molecular weight of the epoxy resin is the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

<(E) Reactive diluent>
The photosensitive resin composition may further contain (E) a reactive diluent. Photoreactivity can be improved by including the component (E). Component (E) can be, for example, a photosensitive (meth)acrylate compound that is liquid, solid or semi-solid at room temperature and has one or more (meth)acryloyl groups in one molecule. Room temperature represents about 25°C. A "(meth)acryloyl group" refers to an acryloyl group and a methacryloyl group.

Representative photosensitive (meth)acrylate compounds include, for example, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate, glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol. Mono- or diacrylates, acrylamides such as N,N-dimethylacrylamide and N-methylolacrylamide, aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate, trimethylolpropane, pentaerythritol and dipentaerythritol. polyhydric acrylates of ethylene oxide, propylene oxide or ε-caprolactone adducts thereof, phenols such as phenoxy acrylate and phenoxyethyl acrylate, or acrylates such as ethylene oxide or propylene oxide adducts thereof, trimethylolpropane Epoxy acrylates derived from glycidyl ethers such as triglycidyl ethers, melamine acrylates, and/or methacrylates corresponding to the above acrylates. Among these, polyvalent acrylates or polyvalent methacrylates are preferable. For example, trivalent acrylates or methacrylates include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane EO-added tri(meth)acrylate, glycerin PO-added tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetrafurfuryl alcohol oligo(meth)acrylate, ethyl carbitol oligo(meth)acrylate, 1,4-butanediol Oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate ) acrylates, N,N,N′,N′-tetrakis(β-hydroxyethyl)ethyldiamine (meth)acrylic acid esters, and trivalent or higher acrylates or methacrylates include tri(2- (Meth)acryloyloxyethyl)phosphate, tri(2-(meth)acryloyloxypropyl)phosphate, tri(3-(meth)acryloyloxypropyl)phosphate, tri(3-(meth)acryloyl-2-hydroxyloxypropyl) Phosphate, di(3-(meth)acryloyl-2-hydroxyloxypropyl)(2-(meth)acryloyloxyethyl)phosphate, (3-(meth)acryloyl-2-hydroxyloxypropyl)di(2-(meth) Phosphoric acid triester (meth)acrylates such as acryloyloxyethyl)phosphate may be mentioned. Any one of these photosensitive (meth)acrylate compounds may be used alone, or two or more thereof may be used in combination.

When the content of component (E) is blended, the total solid content of the photosensitive resin composition is 100% by mass from the viewpoint of promoting photocuring and suppressing stickiness when cured. , preferably 0.5% to 10% by mass, more preferably 2% 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 including the component (G). (G) Examples of organic solvents include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, and propylene glycol. glycol ethers such as monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate and ethyl diglycol acetate; Aliphatic hydrocarbons such as octane and decane, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. These are used individually by 1 type or in combination of 2 or more types. When using an organic solvent, the content can be appropriately adjusted from the viewpoint of coating properties of the photosensitive resin composition.

<(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 impaired. (G) Other additives include, for example, thermoplastic resins, organic fillers, fine particles such as melamine and organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, Colorants such as naphthalene black, polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol and pyrogallol, thickeners such as bentone and montmorillonite, silicone-based, fluorine-based, and vinyl resin-based defoaming agents, Flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus compounds, aromatic condensed phosphate esters, halogen-containing condensed phosphate esters, phenolic curing agents, heat such as cyanate ester curing agents Various additives such as curable resins can be added.

The photosensitive resin composition is prepared by mixing the above (A) to (D) components as essential components, and appropriately mixing the above (E) to (G) components as optional components. The resin varnish can be produced by kneading or stirring with kneading means such as a ball mill, bead mill or sand mill, or stirring means such as a super mixer or planetary mixer.

<Physical properties and uses of the photosensitive resin composition>
A cured product obtained by photocuring the photosensitive resin composition of the present invention and then heat-curing it at 190° C. for 90 minutes exhibits a low average coefficient of linear thermal expansion. That is, an insulating layer and a solder resist having a low average linear thermal expansion coefficient are obtained. 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. Although the lower limit is not particularly limited, it may be 10 ppm or more. The average linear thermal expansion coefficient can be measured according to the method described in <Measurement of Average Linear Thermal Expansion> below.

The photosensitive resin composition of the present invention contains the component (B) having an average particle size and a specific surface area within a predetermined range, so that even if the content of the component (B) is high, the resolution is excellent. characteristics. Therefore, the minimum via diameter with no residue is preferably 100 μm or less, more preferably 90 μm or less, even more preferably 80 μm or less and 70 μm or less. Although the lower limit is not particularly limited, it may be 0.1 μm or more. In addition, since the resolution is excellent, there is usually no resin filling or peeling between L/S (line/space). Although the lower limit is not particularly limited, it may be 1 μm/1 μm or more. Evaluation of resolution can be performed according to the method described in <Evaluation of Resolution and Crack Resistance> below.

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 excellent crack resistance. That is, it provides an insulating layer and a solder resist having excellent crack resistance. Cracks and peeling are usually not observed even after repeating the heating test between −65° C. and 150° C. 500 times. Crack resistance can be evaluated according to the method described in <Evaluation of Resolution and Crack Resistance> below.

Applications of the photosensitive resin composition of the present invention are not particularly limited. It can be used in a wide range of applications requiring a photosensitive resin composition, such as solder resists, underfill materials, die bonding materials, semiconductor encapsulation materials, hole-filling resins, component-embedding resins, and the like. Among them, a photosensitive resin composition for an insulating layer of a printed wiring board (a printed wiring board having a cured product of a photosensitive resin composition as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a photosensitive resin composition Printed wiring board with a cured product as an interlayer insulating layer), photosensitive resin composition for plating (printed wiring board in which plating is formed on the cured product of the photosensitive resin composition), and photosensitive resin composition for solder resist It can be suitably used as a product (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 is coated on a support substrate in a resin varnish state, and the organic solvent is dried to form a photosensitive resin composition layer, whereby a photosensitive film can be obtained. Alternatively, a photosensitive film preliminarily formed on a support may be used by being laminated on the support substrate. The photosensitive film can be laminated to various supporting substrates. Examples of the support substrate mainly include substrates such as glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates.

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

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

Commercially available supports include, for example, 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 Limited. Polyethylene terephthalate films such as the PS series, etc., but not limited to these. In order to facilitate removal of the photosensitive resin composition layer, these supports are preferably coated with a release agent such as a silicone coating agent on the surface. The thickness of the support is preferably in the range of 5 μm to 50 μm, more preferably in the range of 10 μm to 25 μm. By setting the thickness to 5 μm or more, it is possible to suppress breakage of the support when the support is peeled off before development. Resolution can be improved. Also preferred are supports with low fisheyes. Here, fisheye refers to foreign substances, undissolved substances, oxidized substances, etc. of the material being incorporated into the film when the film is produced by heat-melting the material, kneading, extruding, biaxial stretching, casting, etc. It is a thing.

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

By protecting the photosensitive resin composition layer side of the support-attached photosensitive film with a protective film, it is possible to prevent dust from adhering to the surface of the photosensitive resin composition layer and scratches on the surface of the photosensitive resin composition layer. As the protective film, a film made of the same material as the support can be used. Although the thickness of the protective film is not particularly limited, it is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, even more preferably in the range of 10 μm to 30 μm. 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 tends to be improved. The protective film preferably has a lower adhesive strength between the photosensitive resin composition layer and the protective film than the adhesive strength between the photosensitive resin composition layer and the support.

The support-attached photosensitive film of the present invention can be produced, for example, by preparing a resin varnish by dissolving the photosensitive resin composition of the present invention in an organic solvent, applying the resin varnish on the support, and heating or blowing with hot air. It can be produced by drying the organic solvent to form a photosensitive resin composition layer. Specifically, first, after completely removing bubbles in the photosensitive resin composition by a vacuum defoaming method or the like, the photosensitive resin composition is applied onto a support, and the solvent is removed in a hot air oven or a far-infrared oven. A support-attached photosensitive film can be produced by removing, drying, and optionally laminating a protective film on the obtained photosensitive resin composition layer. Specific drying conditions vary depending on the curability of the photosensitive resin composition and the amount of organic solvent in the resin varnish. can be dried for 3 to 13 minutes. The amount of 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 diffusion of the organic solvent in subsequent steps. It is more preferable to make it 2% by mass or less. A person skilled in the art can appropriately set suitable drying conditions by simple experiments. 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. , more preferably 10 μm to 200 μm, more preferably 15 μm to 150 μm, even more preferably 20 μm to 100 μm, and most preferably 20 μm to 60 μm.

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

The photosensitive resin composition layer of the support-attached photosensitive film of the present invention exhibits excellent flexibility. Even if the photosensitive resin composition layer is cut out with a cutter knife, it is preferable that no scattering or cracking of the photosensitive resin composition is observed. It is preferable that no scattering or cracks are observed. Flexibility can be measured according to the description of <Appearance of Film, Evaluation of Flexibility> below.

[Printed wiring board]
The printed wiring board of the present invention includes an insulating layer formed from 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 using the above-described photosensitive film or photosensitive film with a support. A case where the insulating layer is a solder resist will be described below.

<Coating and drying process>
A photosensitive film is formed on the circuit board by applying the photosensitive resin composition in a resin varnish state directly onto the circuit board and drying the organic solvent.

Examples of circuit substrates include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. Here, the term "circuit board" refers to a board having a patterned conductor layer (circuit) formed on one side or both sides of the board as described above. In addition, in a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, a substrate in which one or both sides of the outermost layer of the multilayer printed wiring board is a patterned conductor layer (circuit) is also included here. included in the circuit board. The surface of the conductor layer may be roughened in advance by blackening treatment, copper etching, or the like.

As a coating method, screen printing is generally used for full surface printing, but any other coating method may be used as long as it can be applied uniformly. For example, spray coating method, hot melt coating method, bar coating method, applicator method, blade coating method, knife coating method, air knife coating method, curtain flow coating method, roll coating method, gravure coating method, offset printing method, dip coating method. , brushing, or any other conventional application method can be used. After coating, drying is performed in a hot air oven, a far infrared oven, or the like, if necessary. The drying conditions are preferably 80° C. to 120° C. for 3 minutes to 13 minutes. Thus, a photosensitive film is formed on the circuit board.

<Lamination process>
When a photosensitive film with a support is used, the photosensitive resin composition layer side is laminated on one side or both sides of a circuit board using a vacuum laminator. In the lamination step, when the photosensitive film with a support has a protective film, after removing the protective film, the photosensitive film with a support and the circuit board are preheated as necessary, and the photosensitive resin composition The material layer is press-bonded to the circuit board while being pressurized and heated. In the support-attached photosensitive film, a method of laminating on a circuit board under reduced pressure by a vacuum lamination method is preferably used.

The conditions of the lamination step are not particularly limited, but for example, the pressure bonding temperature (laminating temperature) is preferably 70° C. to 140° C., and the pressure bonding pressure is preferably 1 kgf/cm ² to 11 kgf/cm ² (9. 8×10 ⁴ N/m ² to 107.9×10 ⁴ N/m ² ), the pressure bonding time is preferably 5 seconds to 300 seconds, and the air pressure is 20 mmHg (26.7 hPa) or less. is preferred. Moreover, the lamination process may be of a batch type or a continuous type using rolls. A vacuum lamination method can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nikko Materials, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a roll-type dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. be able to. Thus, a photosensitive film is formed on the circuit board.

<Exposure process>
After the photosensitive film is provided on the circuit board by the coating and drying process or the laminating process, a predetermined portion of the photosensitive resin composition layer is then irradiated with actinic rays through the mask pattern to determine the photosensitivity of the irradiated portion. An exposure step for photocuring the resin composition layer is performed. Actinic rays include, for example, ultraviolet rays, visible rays, electron beams, X-rays, and the like, and ultraviolet rays are particularly preferred. The dose of ultraviolet rays is about 10 mJ/cm ² to 1000 mJ/cm ² . The exposure method includes a contact exposure method in which a mask pattern is brought into close contact with a printed wiring board and a non-contact exposure method in which a parallel light beam is used for exposure without close contact. Either method may be used. Further, when a support exists on the photosensitive resin composition layer, exposure may be performed from above the support, or exposure may be performed after peeling off the support.

Since the solder resist uses the photosensitive resin composition of the present invention, it has excellent resolution. Therefore, as the exposure pattern in the mask pattern, for example, the ratio (L/S) of the circuit width (line; L) and the width (space; S) between the circuits 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. It should be noted that the pitch need not be the same throughout the circuit board.

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

In the case of the wet development, a safe and stable developing solution with good operability such as an alkaline aqueous solution, an aqueous developer, an organic solvent, etc. is used as the developing solution. As a developing method, known methods such as spraying, rocking immersion, brushing, scraping, and the like are 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; and sodium phosphate. , alkali metal phosphates such as potassium phosphate, aqueous solutions of alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, and aqueous solutions of organic bases containing no metal ions 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.
Surfactants, antifoaming agents and the like can be added to these alkaline aqueous solutions in order to improve the developing effect. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8-12, more preferably in the range of 9-11. Further, 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 according to the developability of the photosensitive resin composition layer, but is preferably 20°C to 50°C.

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

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

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

<Thermal curing (post-baking) process>
After the development process is completed, a heat curing (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, a heating process using a clean oven, and the like. In the case of irradiating with ultraviolet rays, the irradiation amount can be adjusted as necessary, for example, irradiation can be performed at an irradiation amount of about 0.05 J/cm ² to 10 J/cm ² . The heating conditions may be appropriately selected according to the type and content of the resin component in the photosensitive resin composition, preferably 150° C. to 220° C. for 20 minutes to 180 minutes, more preferably It is selected in the range of 160° C. to 200° C. for 30 minutes to 120 minutes.

<Other processes>
After forming the solder resist, the printed wiring board may further include a drilling step and a desmear step. These steps may be carried out according to various methods known to those skilled in the art for use in manufacturing printed wiring boards.

After forming the solder resist, if desired, the solder resist formed on the circuit board is subjected to a drilling step to form via holes and through holes. The drilling step can be carried out by a known method such as drilling, laser, plasma, or a combination of these methods if necessary, but a drilling step using a laser such as a carbon dioxide gas laser or a YAG laser is preferred.

A desmear process is a process of desmearing. Resin residue (smear) generally adheres to the inside of the opening formed in the drilling process. Since such smears cause electrical connection failures, processing for removing smears (desmear processing) is performed in this step.

Desmearing may be performed by dry desmearing, wet desmearing, or a combination thereof.

Dry desmearing includes, for example, desmearing using plasma. Desmearing using plasma can be performed using a commercially available plasma desmearing device. Among commercially available plasma desmear treatment apparatuses, suitable examples for use in manufacturing printed wiring boards include a microwave plasma apparatus manufactured by Nissin Co., Ltd., and an atmospheric pressure plasma etching apparatus manufactured by Sekisui Chemical Co., Ltd., and the like.

Examples of wet desmear treatment include desmear treatment using an oxidizing agent solution. When the desmear treatment is performed using the oxidant solution, it is preferable to perform the swelling treatment with the swelling liquid, the oxidation treatment with the oxidant solution, and the neutralization treatment with the neutralization 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 carried out by immersing the substrate having via holes and the like formed therein in a swelling liquid heated to 60° C. to 80° C. for 5 to 10 minutes. As the oxidizing agent solution, an aqueous alkaline permanganate solution is preferable. For example, a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be mentioned. The oxidation treatment with the oxidizing agent solution is preferably carried out 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 Security P" manufactured by Atotech Japan. The neutralization treatment with the neutralizing solution is preferably carried out by immersing the substrate after the oxidation treatment in the neutralizing solution at 30° C. to 50° C. for 3 to 10 minutes. As the neutralizing liquid, an acidic aqueous solution is preferable, and commercially available products include, for example, "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 an interlayer insulating layer, it can be carried out in the same manner as in the case of the solder resist, and after the thermosetting process, the drilling process, the desmear process, and the plating process may be carried out.

A plating process is a process of forming a conductor layer on an insulating layer. The conductor layer may be formed by combining electroless plating and electrolytic plating, or by forming a plating resist having a pattern opposite to that of the conductor layer and forming the conductor layer only by electroless plating. As a method for subsequent pattern formation, for example, a subtractive method, a semi-additive method, or the like known to those skilled in the art can be used.

[Semiconductor device]
A semiconductor device 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 semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

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. A "conducting part" is a "part where an electric signal is transmitted on a printed wiring board", and the place may be a surface or an embedded part. Also, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting the semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively. Examples include a mounting method using a buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, "a mounting method using a build-up layer without bumps (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected." is.

EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by 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, and "Sciqas series" manufactured by Sakai Chemical Industry. , "Seahoster Series" manufactured by Nippon Shokubai Co., Ltd. alone or in combination, subjected to surface treatment with an aminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573), and classified.
Inorganic filler 6 is obtained by performing the same surface treatment as inorganic fillers 1 to 5 using alumina (“AZ series” and “AX series” manufactured by Nippon Steel & Sumikin Materials Co., Ltd.) and classifying. .
Inorganic filler 7 is obtained by performing the same surface treatment as inorganic fillers 1 to 5 using barium sulfate (“B series” and “BF series” manufactured by Sakai Chemical Industry Co., Ltd.) and classifying it. .
Inorganic fillers 1 to 7 were measured for particle size distribution and specific surface area by the following methods.

50 mg of inorganic filler 1 powder, 2 g of a nonionic dispersant (“T208.5” manufactured by NOF Corporation), and 40 g of pure water were weighed into 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 particle size distribution analyzer (LA-950, manufactured by Horiba, Ltd.), and the average particle size and _D90 were calculated. The average particle diameters of the inorganic fillers 2 to 7 were similarly calculated.

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). The specific surface areas of the inorganic fillers 2 to 7 were similarly measured.
The average particle size and 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 A-1 component)
162 parts of 1,1′-bis(2,7-diglycidyloxynaphthyl)methane with an epoxy equivalent of 162 (“EXA-4700”, manufactured by Dainippon Ink and Chemicals) was added to a gas inlet tube, a stirring device, and a cooling tube. The mixture was placed in a flask equipped with a thermometer, 340 parts of carbitol acetate was added and dissolved by heating, and 0.46 parts 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 80-90° C., 80 parts of tetrahydrophthalic anhydride was added, reacted for 8 hours, and cooled. In this manner, a resin solution (non-volatile content 70%, hereinafter abbreviated as “A-1”) having a solid matter acid value of 90 mgKOH/g was obtained.

<Examples 1 to 7, Comparative Examples 1 to 4>
A resin varnish was prepared by blending each component in the blending ratio shown in the table below and using a high-speed rotating mixer. Next, as a support, a PET film (“Lumirror T6AM” manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C., “release type PET") was prepared. The prepared resin varnish is evenly applied to the release PET with a die coater so that the thickness of the photosensitive resin composition layer after drying is 40 μm, and dried at 80 ° C. to 110 ° C. for 6 minutes. A support-attached photosensitive film having a photosensitive resin composition layer on the mold PET was obtained.

A measurement method and an evaluation method in physical property evaluation will be described.

<Evaluation of Appearance and Flexibility of Film>
The appearance of the photosensitive resin composition layer of the support-attached photosensitive film produced in Examples and Comparative Examples was visually observed. Also, when the photosensitive resin composition layer was cut out with a utility knife, the scattering of the resin and the occurrence of cracks were visually observed. Furthermore, the occurrence of cracks when the support-attached photosensitive film was bent 180° was visually observed and evaluated according to the following criteria.
◯: No cissing or unevenness, and no resin scattering or cracks observed.
x: Repellency, unevenness, scattering of resin, or cracks are observed.

<Measurement of average linear thermal expansion coefficient>
(Formation of cured product for evaluation)
The photosensitive resin composition layers of the support-attached photosensitive films obtained in Examples and Comparative Examples were exposed to ultraviolet light at 100 mJ/cm ² to be photocured. After that, the entire surface of the photosensitive resin composition layer was developed by spraying a 1% by mass sodium carbonate aqueous solution at 30° C. as a developer at a spray pressure of 0.2 MPa for 2 minutes. After spray development, 1 J/cm ² ultraviolet irradiation was performed, and further heat treatment was performed at 190° C. for 90 minutes to obtain a cured product. After that, 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 apparatus, the measurement was performed twice continuously under the measurement conditions of a load of 1 g and a temperature increase rate of 5° C./min. An 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 laminate for evaluation)
The copper layer of a glass epoxy substrate (copper clad laminate) on which a circuit is formed by patterning a copper layer with a thickness of 18 μm is treated with a surface treatment agent (CZ8100, manufactured by MEC Co., Ltd.) containing an organic acid to roughen it. changed. Next, the photosensitive resin composition layer of the support-attached photosensitive film obtained in Examples and Comparative Examples is placed in contact with the surface of the copper circuit, and a vacuum laminator (VP160, manufactured by Nikko Materials Co., Ltd.) is used. Lamination was performed to form a laminate in which the copper-clad laminate, the photosensitive resin composition layer, and the support were laminated in this order. The crimping conditions were as follows: evacuation time of 30 seconds, crimping temperature of 80° C., crimping pressure of 0.7 MPa, and pressurization time of 30 seconds. The laminate was allowed to stand at room temperature for 30 minutes or longer, and the support of the laminate was exposed to ultraviolet light using a pattern forming apparatus using a round hole pattern. Exposure pattern: aperture: 50 μm/60 μm/70 μm/80 μm/90 μm/100 μm round hole, 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 for drawing lines and spaces of /100 μm was used. After standing at room temperature for 30 minutes, the support was peeled off from the laminate. The entire surface of the photosensitive resin composition layer on the laminate was developed by spraying a 1% by mass sodium carbonate aqueous solution at 30° C. as a developer at a spray pressure of 0.2 MPa for 2 minutes. After spray development, ultraviolet irradiation was performed at 1 J/cm ² , and heat treatment was performed at 180° C. for 30 minutes to cure the photosensitive resin composition layer, thereby forming an insulating layer having openings on the laminate. . This was used as a laminate for evaluation.

(Evaluation of resolution)
A round hole formed by patterning in the laminate for evaluation was observed with an SEM (magnification: 1000), and the minimum via diameter with no residue and the minimum L/S with no clogging or peeling were measured. When there was no minimum L/S with no resin filling or peeling, it was marked as "x". Also, the L/S shape was evaluated according to the following criteria.
◯: L/S at three points was observed, and there was no peeling or filling between all L/S.
x: Observation of L/S at three points, resin filling or peeling observed between any L/S.

(Evaluation of crack resistance)
After exposing the laminate for evaluation in the air at −65° C. for 15 minutes, the temperature was raised at a temperature increase rate of 180° C./min, and then exposed in the air at 150° C. for 15 minutes, followed by 180° C./min. was repeated 500 times. After the test, the degree of cracks and peeling of the substrate for evaluation was observed with an optical microscope (manufactured by Nikon Corporation, "ECLIPSE LV100ND") and evaluated according to the following criteria.
Good: No cracks or peeling observed.
x: Cracks and peeling are observed.

Abbreviations, etc. 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-1 component synthesized in Synthesis Example 1 (non-volatile content 70%)
(B) Component/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
(C) Component Irgacure 819: Bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by BASF)
(D) Component NC3000H: Biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 272)
・ 1031S: Tetrakis hydroxyphenyl ethane type epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 200)
(E) Component DPHA: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., acrylic equivalent of about 96)
(F) component 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 film appearance, flexibility, resolution, crack resistance, and a low average coefficient of linear thermal expansion.

On the other hand, in Comparative Example 1, in which the content of the inorganic filler exceeds 85% by mass, the appearance, flexibility and resolution of the film were poor 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. In addition, the crack resistance was poor and could not be used as a photosensitive resin composition. Comparative Example 3, which uses an 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, has a high average linear thermal expansion coefficient because the component (B) cannot be sufficiently filled. . Moreover, the appearance, flexibility, resolution, and crack resistance of the film were poor, and it could not be used as a photosensitive resin composition. In Comparative Example 4, which uses an inorganic filler having a specific surface area of less than 1.4 m ² /g, the minimum via diameter exceeds 100 μm due to poor resolution, and it cannot be used as a photosensitive resin composition. I didn't.

In each example, it was confirmed that even if the components (E) to (F) and the like were not contained, the results were similar to those of the above examples, albeit to varying degrees.

Claims (15)

(A) a resin containing an ethylenically unsaturated group and a carboxyl group;
(B) Average particle diameter (d50) is 0.5 μm or more and 2.5 μm or less, particle diameter (D90) is 0.5 μm or more and 5.5 μm or less, and specific surface area is 1.4 m ² /g or more and 10 m ² / g or less inorganic filler,
(C) a photopolymerization initiator, and (D) a photosensitive resin composition containing an epoxy resin,
(B) component is surface-treated with a silane coupling agent,
(B) The content of the component 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,
(D) component contains at least one of a biphenyl-type epoxy resin and a tetraphenylethane-type epoxy resin,
The average particle size (d50) of the component (B) is the particle size at which the cumulative frequency of the volume-based particle size distribution measured by a laser diffraction/scattering particle size distribution analyzer is 50%.
The particle size (D90) of the component (B) is the particle size at which the cumulative frequency of the volume-based particle size distribution measured by a laser diffraction/scattering particle size distribution analyzer is 90%.
(B) The photosensitive resin composition, wherein the specific surface area of the component is a specific surface area obtained by measurement with a BET fully automatic specific surface area measuring device. The average linear thermal expansion coefficient at 25 ° C. to 150 ° C. of the cured product obtained by photocuring the photosensitive resin composition for 90 minutes at 190 ° C. is 10 ppm or more and 45 ppm or less according to claim 1. A photosensitive resin composition. 3. The photosensitive resin composition according to claim 1, wherein component (A) has a naphthalene skeleton. The photosensitive resin composition according to any one of claims 1 to 3, wherein component (A) is an acid-modified naphthalene skeleton-containing epoxy (meth)acrylate. The photosensitive resin composition according to any one of claims 1 to 4, wherein component (D) comprises a biphenyl type epoxy resin. 6. The photosensitive resin composition according to any one of claims 1 to 5, wherein component (B) has a specific surface area of 6.3 m ² /g or more and 10 m ² /g or less. The photosensitive resin composition according to any one of claims 1 to 6, wherein the component (B) contains silica. The content of component (A) is 5% by mass or more and 25% by mass or less when the total solid content of the photosensitive resin composition is 100% by mass, according to any one of claims 1 to 7. A photosensitive resin composition. The content of component (C) is 0.01% by mass or more and 1% by mass or less when the total solid content of the photosensitive resin composition is 100% by mass, according to any one of claims 1 to 8 The photosensitive resin composition described. The content of component (D) is 1% by mass or more and 25% by mass or less when the total solid content of the photosensitive resin composition is 100% by mass, according to any one of claims 1 to 9 A photosensitive resin composition. A photosensitive film containing the photosensitive resin composition according to any one of claims 1 to 10. A photosensitive film with a support, comprising a support and a photosensitive resin composition layer containing the photosensitive resin composition according to any one of claims 1 to 10 provided on the support. A printed wiring board comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of claims 1 to 10. 14. The printed wiring board according to claim 13, wherein the insulating layer is solder resist. A semiconductor device comprising the printed wiring board according to claim 13 or 14.