JP7078065B2 - 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 the printed wiring board, a solder resist may be provided as a permanent protective film for suppressing the adhesion of solder to the portion where the solder is unnecessary and for suppressing the corrosion of the circuit board. As the solder resist, for example, a photosensitive resin composition as described in Patent Document 1 is generally used.

Japanese Unexamined Patent Publication No. 2011-164304

Photosensitive resin compositions for solder resists generally have resolution, insulation, solder heat resistance, gold plating resistance, moisture heat resistance, crack resistance (TCT resistance), and ultra-accelerated high temperature between fine wiring. HAST resistance to high humidity life test (HAST) is required. In recent years, in response to the increase in the 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 have further durability.

In order to increase the crack resistance, for example, a method of highly filling the photosensitive resin composition with an inorganic filler can be considered, but the adhesion to the adherend is lowered and the light transmission is not sufficient. There is a possibility that the sensitivity of the bottom will deteriorate and undercut will occur, or that the opening will not be sufficient due to halation of light.

Further, from the viewpoint of productivity, it is required that the solder resist is less likely to be cracked during handling and is less likely to be cracked or scattered when the solder resist is cut.

The subject of the present invention is a photosensitive resin composition which is excellent in crack resistance, can obtain a cured product having a low average coefficient of linear thermal expansion, and is excellent in the appearance, flexibility, and resolution of a film when formed into a film. The present invention 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 diligent studies to solve the above problems, the present inventors have made a photosensitive resin composition containing an inorganic filler having a predetermined average particle size and a predetermined specific surface area to obtain resolution and crack resistance. Further, they have found that the appearance and flexibility of the 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.
(B) A photosensitive resin composition having a component content of 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 of the cured product obtained by photo-curing the photosensitive resin composition at 190 ° C. for 90 minutes at 25 ° C. to 150 ° C. is 10 ppm or more and 45 ppm or less [1]. 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 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 one of a biphenyl type epoxy resin and a tetraphenyl ethane 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] Photosensitivity with a support having 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 of a 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 coefficient of linear thermal expansion, and a photosensitive resin composition having excellent appearance, flexibility, and resolution when formed into a film. A 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.

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 has (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 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, it is 60% by mass or more and 85% by mass or less.

By incorporating the components (A) to (D) in the photosensitive resin composition, a cured product having excellent crack resistance and a low average coefficient of linear thermal expansion can be obtained, and the film when formed into a film can be obtained. A photosensitive resin composition having excellent 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. 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 propagyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadiimide group and a (meth) acrylic group, and examples thereof include reactivity of 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.

The component (A) is not particularly limited as long as it is a compound having an ethylenically unsaturated group and a carboxyl group and capable of photoradical polymerization and alkaline development, but the carboxyl group and 2 in one molecule are not particularly limited. A resin having more than one ethylenically unsaturated group is preferable.

One embodiment 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 reacting with an acid anhydride. Specifically, an unsaturated carboxylic acid is reacted with an epoxy compound to obtain an unsaturated epoxy ester resin, and an unsaturated epoxy ester resin is reacted with an acid anhydride to obtain an acid-modified unsaturated epoxy ester resin.

As the epoxy compound, any compound having an epoxy group in the molecule can be used. For example, a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a hydrogenated bisphenol F type epoxy resin can be used. , Biphenol type epoxy resin, modified bisphenol F type epoxy resin modified to trifunctional or higher by reacting bisphenol S type epoxy resin, bisphenol F type epoxy resin; biphenol type epoxy resin, tetramethylbiphenol type, etc. Biphenol type epoxy resin; Novolak type epoxy resin such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type novolak type epoxy resin, alkylphenol novolak type epoxy resin; bisphenol AF type epoxy resin, and perfluoroalkyl type epoxy 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 a naphthalene skeleton (naphthalene skeleton-containing epoxy resin) such as naphthalene type epoxy resin obtained by condensation reaction of hydroxynaphthalene and aldehydes; bixirenol type epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin Tert-Butyl-catechol type epoxy resin; epoxy resin containing a fused 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 Structural epoxy resin; 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 , Glycidyl group-containing acrylic resin such as a copolymer of glycidyl methacrylate and acrylic acid ester; fluorene type epoxy resin; 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 aromatics and aromatic heterocycles. Of these, 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 novolac type epoxy resin, and a glycidyl ester type epoxy resin are preferable. Above all, 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 rate of the cured product is further lowered. A skeleton-containing epoxy resin, a condensed ring skeleton-containing epoxy resin, and a biphenyl type epoxy resin are more preferable, and a naphthalene skeleton-containing epoxy resin is further preferable. 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 between polyhydroxynaphthalene and aldehydes are preferable.

Examples of the dihydroxynaphthalene type epoxy resin include 1,3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, 1,6-diglycidyloxynaphthalene, and 2,3-di. 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, and the like. Examples thereof include 1,1'-bee (2,7-diglycidyloxy) naphthyl and the like.

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

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 between polyhydroxynaphthalene and aldehydes are preferable, and an epoxy in one molecule is particularly preferable. 1,1'-bis (2,7-diglycidyloxynaphthyl) methane having three 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 rate. It is preferable because it has excellent heat resistance.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid and the like, and these may be used alone or in combination of two or more. Of these, 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", where the epoxy group of the epoxy compound is referred to as "epoxy (meth) acrylate". It is substantially extinguished by the reaction with (meth) acrylic acid. "(Meta) acrylate" refers to methacrylate and acrylate. Acrylic acid and methacrylic acid are sometimes collectively referred to as "(meth) acrylic acid".

Examples of the acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic acid dianhydride. Anhydrous and the like can be mentioned, and any one of them may be used alone or two or more thereof 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 and an acid anhydride are reacted. It is also good. Further, if necessary, a solvent or a polymerization inhibitor may be used.

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 the structure derived from the above-mentioned epoxy compound. 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 derives 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 lowering 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 with (meth) acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. ..

Commercially available products can be used for such acid-modified unsaturated epoxy ester resins, and specific examples thereof include "ZAR-2000" (bisphenol A type epoxy resin, acrylic acid, and succinic anhydride) manufactured by Nippon Kayaku Co., Ltd. (Reactant), "ZFR-1491H", "ZFR-1533H" (reactant of bisphenol F type epoxy resin, acrylic acid, and tetrahydrophthalic anhydride), "PR-300CP" (cresol novolac type epoxy) manufactured by Showa Denko Co., Ltd. (Reactants of resins, acrylic acids, and acid anhydrides) 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 the (meth) acrylic resin having a structural unit obtained by polymerizing (meth) acrylic acid. An unsaturated modified (meth) acrylic resin obtained by reacting and introducing an ethylenically unsaturated group can be mentioned. 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 the 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.

Commercially available products can be used for such unsaturated modified (meth) acrylic resins, and specific examples thereof include "SPC-1000" and "SPC-3000" manufactured by Showa Denko KK and "Cyclomer" manufactured by Daisel 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 even more 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 even more preferably 7,500 or less. The weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

The acid value of the component (A) is preferably 0.1 mgKOH / g or more, preferably 0.5 mgKOH / g or more, from the viewpoint of improving the alkali developability of the photosensitive resin composition. 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, and more preferably 120 mgKOH / g or less, from the viewpoint of suppressing the dissolution of the fine pattern of the cured product by development and improving the 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 group present in the component (A), and the acid value can be measured by the following method. First, about 1 g of the measurement 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 0.1 N 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 the acid value (mgKOH / g), Vf represents the titration amount (mL) of KOH, Wp represents the mass of the measured resin solution (g), and I represents the non-volatile content of the measured resin solution. Represents the ratio (mass%) of.

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

From the viewpoint of improving the alkali developability, the content of the component (A) is preferably 5% by mass or more, preferably 8% by mass or more, when the total solid content of the photosensitive resin composition is 100% by mass. It is 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 (B) contains 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 becomes possible to provide a photosensitive resin composition capable of obtaining a cured product having a low average linear thermal expansion coefficient.

The material of the inorganic filler is not particularly limited, but 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 zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like. Among these, silica, alumina and barium sulfate are preferable, and silica is particularly preferable. Further, as silica, spherical silica is preferable. The inorganic filler 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 linear thermal expansion coefficient. 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 products having such an average particle size include "Admafine" manufactured by Admatex, "SFP series" manufactured by Electrochemical Industry Co., Ltd., and "SP (H) series" manufactured by Nippon Steel & Sumikin Materials Co., Ltd. "Sciqas series" manufactured by Sakai Chemical Industry Co., Ltd., "Seahoster series" manufactured by Nippon Catalyst Co., Ltd., etc., and "AZ series", "AX series" manufactured by Nippon Steel & Sumikin Materials Co., Ltd., etc. are listed as commercial products of alumina. Examples of commercially available barium sulfate products 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 the Mie scattering theory. Specifically, a laser diffraction / scattering type particle size distribution measuring device is used to create a particle size distribution of an inorganic filler on a volume basis, and the particle size at which the cumulative frequency is 50% (d50) is used as the average particle size for measurement. 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 type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd., "SALD-2200" manufactured by Shimadzu Corporation, or 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. , 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 in the same manner as the average particle size.

By classifying the inorganic filler with a classifier or the like, an inorganic filler having a desired average particle size can be obtained.

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 the inorganic filler).

From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane compound, an organosilazane compound, and titanate. It is preferable that the treatment is performed 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., and Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., 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. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m ² or more, more preferably 0.1 mg / m ^{2 or more, and 0.2 mg / m 2 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 an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 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 preferable. 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 (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon 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. or the like can be used.

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, 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. The upper limit is 85% by mass or less, preferably 80% by mass or less, and more preferably 70% by mass or less from the viewpoint of suppressing light reflection.

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

The component (C) is not particularly limited, but is, for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl). ) Methyl]-[4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, etc. Photopolymerization initiator; Oxyme ester-based photopolymerization initiator such as etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) Benzophenyl, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl- (2,4,6-trimethylbenzoyl) phosphenyl oxide, ethyl- (2) , 4,6-trimethylbenzoyl) phenylphosphinate, 4,4'-bis (diethylamino) benzophenone, 1-hydroxy-cyclohexyl-phenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1, -[4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxand and the like. , A sulfonium salt-based photopolymerization initiator and the like can also 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 is combined with the component (C) as a photopolymerization initiation aid, such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, and pentyl-4-. It may contain tertiary amines such as dimethylaminobenzoate, triethylamine, triethanolamine, or may contain photosensitizers such as pyrarizons, anthracenes, coumarins, xanthons, 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 "Omnirad 907", "Omnirad 369", "Omnirad 379", "Omnirad 819", "Omnirad TPO" manufactured by IGM, and "IrgacureOXE-01", "Irgacure" manufactured by BASF. Examples thereof include "N-1919" manufactured by ADEKA Corporation.

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

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

The component (D) includes, for example, a fluorine-containing epoxy resin such as a bisphenol AF type epoxy resin and a perfluoroalkyl type epoxy resin; a bisphenol A type epoxy resin; a bisphenol F type epoxy resin; a bisphenol S type epoxy resin; a bixirenol type. Epoxy resin; Dicyclopentadiene type epoxy resin; Trisphenol type epoxy resin; Naftor novolac type epoxy resin; Phenol novolak type epoxy resin; tert-butyl-catechol type epoxy resin; Naphthalene type epoxy resin; Naftor 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; epoxy resin having a butadiene structure; alicyclic epoxy resin, fat having an 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, bisphenol F type epoxy resin and biphenyl type epoxy resin are preferable, and 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, and tetraphenylethane type epoxy resin are preferable, and tetraphenylethane type epoxy resin is more preferable. .. The epoxy resin may be used alone or in combination of two or more. The component (D) preferably contains at least one of a biphenyl type epoxy resin and a tetraphenylethane type epoxy resin from the viewpoint of improving adhesion and heat resistance.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile 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, and "828US" and "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 & Sumitomo Metal Corporation. (Mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "YD-8125G" manufactured by Nippon Steel & Sumitomo Metal Corporation (bisphenol A type epoxy resin), "EX-721" manufactured by Nagase Chemtex Co., Ltd. (glycidyl ester) Type epoxy resin), "Selokiside 2021P" manufactured by Daicel Co., Ltd. (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure), "ZX1658" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., " "ZX1658GS" (liquid 1,4-glycidylcyclohexane), "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "E-7432", "E-7632" (perfluoroalkyl type epoxy) manufactured by Daikin Industries, Ltd. Resin), DIC's "HP-4700", "HP-4710" (naphthalen type tetrafunctional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy) Resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" , "EXA-7311-G4S", "HP6000" (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" (naphthalen type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), manufactured by Nippon Steel & Sumitomo Metal Corporation. "YSLV-80XY" (tetramethylbisphenol F type epoxy resin), "YX4000H" manufactured by Mitsubishi Chemical Corporation, "Y" "L6121" (biphenyl type epoxy resin), "YX4000HK" (bixirenol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., Mitsubishi Chemical "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "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 showing good tensile fracture strength and insulation reliability. , More preferably 5% by mass or more, still more preferably 8% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.

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

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by the gel permeation chromatography (GPC) method.

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

Typical photosensitive (meth) acrylate compounds include 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, acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, aminoalkylacrylates such as N, N-dimethylaminoethyl acrylate, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. Polyvalent alcohols or polyhydric acrylates of these ethylene oxide, propylene oxide or ε-caprolactone adducts, phenols such as phenoxy acrylates and phenoxyethyl acrylates, or acrylates such as ethylene oxide or propylene oxide adducts thereof, trimethyl propane. Examples thereof include epoxy acrylates derived from glycidyl ethers such as triglycidyl ethers, melamine acrylates, and / or methacrylates corresponding to the above-mentioned acrylates. Among these, polyhydric acrylates or polyvalent methacrylates are preferable, and for example, 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, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, N, N, N', N'-tetrakis (β-hydroxyethyl) ethyldiamine (meth) acrylic acid ester, etc. Examples of trivalent or higher acrylates or methacrylates include tri (2-). (Meta) Acryloyloxyethyl) Phosphate, Tri (2- (Meta) Acryloyloxypropyl) Phosphate, Tri (3- (Meta) Acryloyloxypropyl) Phosphate, Tri (3- (Meta) Acryloyl-2-hydroxyloxypropyl) Phosphate, Di (3- (meth) acryloyl-2-hydroxyloxypropyl) (2- (meth) acryloyloxyethyl) phosphate, (3- (meth) acryloyl-2-hydroxyloxypropyl) di (2- (meth) Phosphate triester (meth) acrylates such as acryloyloxyethyl) phosphate can be mentioned. Any one of these photosensitive (meth) acrylate compounds may be used alone or two or more thereof may be used in combination.

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

<(F) Organic solvent>
The photosensitive resin composition may further contain (G) an organic solvent. The viscosity of the varnish can be adjusted by containing the component (G). Examples of the organic solvent include ketones such as ethylmethylketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methylcellosolve, butylcellosolve, methylcarbitol, butylcarbitol 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, etc. 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. When an organic solvent is used, the content can be appropriately adjusted from the viewpoint of coatability of the photosensitive resin composition.

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

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

<Physical characteristics and uses of photosensitive resin composition>
The cured product obtained by photo-curing the photosensitive resin composition of the present invention and then heat-curing 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, 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 linear expansion rate> described later.

Since 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, the resolution is excellent even if the content of the component (B) is large. It shows the characteristic. Therefore, the minimum via diameter without residue is preferably 100 μm or less, more preferably 90 μm or less, still more preferably 80 μm or less, and 70 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more. Further, since the resolution is excellent, there is usually no resin filling 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 of the photosensitive resin composition of the present invention, which is photo-cured and then heat-cured 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 rise test between -65 ° C and 150 ° C is repeated 500 times, no crack or peeling is usually observed. The crack resistance can be evaluated according to the method described in <Evaluation of resolution and crack resistance> described later.

The application of the photosensitive resin composition of the present invention is not particularly limited, but is limited to photosensitive films, photosensitive films with supports, insulating resin sheets such as prepregs, circuit boards (laminated board applications, multilayer printed wiring board applications, etc.). It can be used in a wide range of applications in which a photosensitive resin composition is required, such as a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, 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) and a photosensitive resin composition for an interlayer insulating layer (a photosensitive resin composition). A printed wiring board with a cured product as an interlayer insulating layer), a photosensitive resin composition for plating (a printed wiring board in which plating is formed on a cured product of the photosensitive resin composition), and a photosensitive resin composition for solder resist. It can be suitably used as a material (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 on a support substrate in a resin varnish state and dried with an organic solvent to form a photosensitive resin composition layer to form a photosensitive film. Further, it is also possible to use a photosensitive film formed on the support in advance by laminating it on the support substrate. The photosensitive film can be laminated on various support substrates. Examples of the support substrate mainly include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a heat-curable polyphenylene ether substrate, 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 provided on the support and formed of the photosensitive resin composition of the present invention.

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 preferable.

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

Further, in order to reduce the scattering of light during exposure by 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), which 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 and scratches. As the protective film, a film made of the same material as the above-mentioned support can be used. The thickness of the protective film is not particularly limited, but 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 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.

For the photosensitive film with a support of the present invention, for example, a resin varnish in which the photosensitive resin composition of the present invention is dissolved in an organic solvent is prepared, the resin varnish is applied onto the support, and heating or hot air blowing is performed. It can be produced 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 onto the support, and the solvent is applied by a hot air furnace or a far-infrared furnace. A photosensitive film with a support can be produced by removing it, drying it, and then laminating a protective film on the obtained photosensitive resin composition layer as needed. Specific drying conditions vary depending on the curability of the photosensitive resin composition and the amount of the organic solvent in the resin varnish, but in the case of the resin varnish containing 30% by mass to 60% by mass of the organic solvent, the temperature is 80 ° C. to 120 ° C. It 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 a later step. It is more preferably 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 the sensitivity and resolution inside the photosensitive resin composition layer. The range is more preferably 10 μm to 200 μm, further preferably 15 μm to 150 μm, further preferably 20 μm to 100 μm, and even more preferably 20 μm to 60 μm.

Examples of the coating method of the photosensitive resin composition include a gravure coat method, a micro gravure coat method, a reverse coat method, a kiss reverse coat method, a die coat method, a slot die method, a lip coat method, a comma coat method, and a blade coat method. Examples thereof include a roll coat method, a knife coat method, a curtain coat method, a chamber gravure coat method, a slot orifice method, a spray coat method, and a dip coat method.
The photosensitive resin composition may be applied in several times, may be applied once, or may be applied in combination of a plurality of different methods. Of these, the die coat method, which is excellent in uniform coatability, is preferable. Further, in order to prevent foreign matter from being mixed in, it is preferable to carry out the coating step in an environment such as a clean room where foreign matter is less generated.

The photosensitive resin composition layer of the photosensitive film with a support of the present invention exhibits a characteristic of being excellent in flexibility. Even if the photosensitive resin composition layer is cut out with a cutter knife, it is preferable that no scattering or cracks are observed in the photosensitive resin composition, and even if the photosensitive resin composition layer is bent 180 °, the photosensitive resin composition is formed. It is preferable that no scattering or cracks are observed. The flexibility can be measured according to the description of <Evaluation of film appearance and flexibility> 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 by 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.

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

Examples of the circuit board include a glass epoxy board, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. Here, the circuit board refers to a board on which a conductor layer (circuit) patterned on one side or both sides of the board is formed as described above. Further, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, a substrate in which one or both sides of the outermost layer of the multilayer printed wiring board is a conductor layer (circuit) in which a pattern is processed is also used here. It is 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 the coating method, full-page printing by a screen printing method is generally used, but any other coating method as long as it can be uniformly coated may be used. For example, spray coat method, hot melt coat method, bar coat method, applicator method, blade coat method, knife coat method, air knife coat method, curtain flow coat method, roll coat method, gravure coat method, offset printing method, dip coat method. , Brush coating, and all other normal coating methods can be used. After application, dry in a hot air oven or far infrared oven if necessary. The drying conditions are preferably 80 ° C. to 120 ° C. for 3 to 13 minutes. In this way, a 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, if 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 as necessary to form a photosensitive resin. The material layer is pressure-bonded to the circuit board while being pressurized and heated. In 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 crimping temperature (laminating temperature) is preferably 70 ° C. to 140 ° C., and the crimping 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 crimping time is preferably 5 to 300 seconds, and the air pressure is 20 mmHg (26.7 hPa) or less for laminating under reduced pressure. Is preferable. 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 a vacuum applicator manufactured by Nikko Materials, a vacuum pressurized laminator manufactured by Meiki Co., Ltd., a roll dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. be able to. In this way, 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 steps or the laminating step, a predetermined portion of the photosensitive resin composition layer is irradiated with active light through a mask pattern to make the irradiated portion photosensitive. An exposure step of photocuring the resin composition layer is performed. Examples of the active ray include ultraviolet rays, visible rays, electron beams, X-rays and the like, and ultraviolet rays are particularly preferable. The irradiation amount of ultraviolet rays is approximately 10 mJ / cm ² to 1000 mJ / cm ² . The exposure method includes a contact exposure method in which the mask pattern is brought into close contact with the printed wiring board and a non-contact exposure method in which the mask pattern is exposed by using parallel rays without being brought into close contact with each other, but either of them may be used. When the support is present on the photosensitive resin composition layer, it may be exposed from above the support or may be exposed after the support is peeled off.

Since the solder resist uses the photosensitive resin composition of the present invention, it has excellent resolution. Therefore, as an exposure pattern in the mask pattern, for example, the ratio (L / S) of the circuit width (line; L) to the width (space; S) between 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. The pitch does not have to be the same throughout the circuit board.

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

In the case of the above wet development, a safe, stable and easy-to-operate developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent is used as the developer, and the developing step using an alkaline aqueous solution is particularly preferable. Further, as a developing method, known methods such as spraying, rocking dipping, brushing, and scraping are appropriately adopted.

Examples of the alkaline aqueous solution used as the developing solution include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and sodium bicarbonate, or bicarbonates and sodium phosphate. , An aqueous solution of an alkali metal phosphate such as potassium phosphate, an aqueous solution of an alkali metal pyrophosphate such as sodium pyrophosphate and 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.
A surfactant, an antifoaming agent, or the like can be added to the developing solution in order to improve the developing effect of these alkaline aqueous solutions. The pH of the alkaline aqueous solution is preferably in the range of, for example, 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 according to the developability of the photosensitive resin composition layer, but is preferably 20 ° C to 50 ° C.

The organic solvent used as the developing solution is, 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, diethylene glycol. It is a 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 an organic solvent can be used alone or in combination of two or more. 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, if necessary, the above-mentioned two or more kinds of development 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, and the like, and the high-pressure spray method is suitable for improving the resolution. When the spray method is adopted, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

<Thermosetting (post-baking) process>
After the development step is completed, a thermosetting (post-baking) step is performed to form a solder resist. Examples of the post-baking step include an ultraviolet irradiation step using a high-pressure mercury lamp and a heating step using a clean oven. When irradiating with ultraviolet rays, the irradiation amount can be adjusted as needed, and for example, irradiation can be performed with 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, 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 30 minutes to 120 minutes at 160 ° C to 200 ° C.

<Other processes>
The printed wiring board may further include a drilling step and a desmear step after forming the solder resist. These steps may be carried out according to various methods known to those skilled in the art, which are used in the manufacture of printed wiring boards.

After forming the solder resist, if desired, a drilling step is performed on the solder resist formed on the circuit board to form via holes and through holes. The drilling step can be performed by, for example, a known method such as a drill, a laser, or plasma, and if necessary, these methods can be combined, but a drilling step using a laser such as a carbon dioxide laser or a YAG laser is preferable.

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

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

Examples of the dry-type desmear treatment include desmear treatment using plasma. The desmear treatment using plasma can be carried out by using a commercially available plasma desmear treatment apparatus. Among the commercially available plasma desmear processing devices, examples suitable for the production of printed wiring boards include a microwave plasma device manufactured by Nissin, a normal pressure plasma etching device manufactured by Sekisui Chemical Co., Ltd., and the like.

Examples of the 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 solution, the oxidation treatment with the oxidant solution, and the neutralization treatment with the neutralizing solution in this order. Examples of the swelling liquid include "Swelling Dip Security Guns P" and "Swelling Dip Security Guns SBU" manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing a substrate on which a via hole or the like is formed in a swelling liquid heated to 60 ° C to 80 ° C for 5 to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganate aqueous solution, and examples thereof include a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. 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 to 30 minutes. Examples of commercially available alkaline permanganate aqueous solutions include "Concentrate Compact CP" and "Dozing 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. 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-type desmear treatment and the wet-type desmear treatment are carried out in combination, the dry-type desmear treatment may be carried out first, or the wet-type desmear treatment may be carried out 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 drilling step, the desmear step, and the plating step may be performed after the thermosetting step.

The plating process is a process of forming a conductor layer on the insulating layer. The conductor layer may be formed by combining electrolytic plating and electrolytic plating, 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 electrolytic plating. As a method for forming a pattern thereafter, for example, a subtractive method or a semi-additive method 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 by using the printed wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, 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. The "conduction point" is a "place where an electric signal is transmitted in a printed wiring board", and the place may be a surface or an embedded place. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method for mounting a semiconductor chip in manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. 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 the bumpless build-up layer (BBUL)" means "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the 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 quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

(Preparation of inorganic filler)
Inorganic fillers 1 to 5 are "Admafine" manufactured by Admatex, "SFP series" manufactured by Denki Kagaku Kogyo, "SP (H) series" manufactured by Nippon Steel & Sumikin Materials, and "Sciqas series" manufactured by Sakai Kagaku Kogyo. , "Sea Hoster Series" manufactured by Nippon Shokubai Co., Ltd., alone or in combination, surface-treated with an aminosilane-based coupling agent (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.), and classified.
The inorganic filler 6 is 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 them. ..
The inorganic filler 7 was obtained by performing the same surface treatment as the inorganic fillers 1 to 5 using barium sulfate (“B series” and “BF series” manufactured by Sakai Chemical Industry Co., Ltd.) and classifying them. ..
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 the nonionic dispersant (“T208.5” manufactured by Nippon Oil & Fats Co., Ltd.), and 40 g of pure water were weighed in a vial and dispersed by ultrasonic waves for 20 minutes. Using a laser diffraction type particle size distribution measuring device (LA-950, manufactured by HORIBA, Ltd.), the particle size distribution was measured by a batch cell method, and the average particle size, D ₉₀ , was calculated. The average particle size of the inorganic fillers 2 to 7 was calculated in the same manner.

The specific surface area of the inorganic filler 1 was measured using a BET fully automatic specific surface area measuring device (Maxorb HM-1210 manufactured by Mountech). The specific surface area of the inorganic fillers 2 to 7 was measured in the same manner.
The results of the average particle size and specific surface area of each inorganic filler are 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 ("EXA-4700", manufactured by Dainippon Ink and Chemicals Co., Ltd.) having an epoxy equivalent of 162 is provided in a gas introduction pipe, agitator, and a cooling pipe. And 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. The mixture was heated to 95-105 ° 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, and the reaction was allowed to cool for 8 hours. In this way, a resin solution having an 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>
Each component was blended in the blending ratio shown in the table below, and a resin varnish was prepared using a high-speed rotary mixer. Next, a PET film (Toray Industries, Inc., "Lumilar T6AM", thickness 38 μm, softening point 130 ° C., “Release”” was released as a support with an alkyd resin-based mold release agent (lintec, “AL-5”). Mold PET ") was prepared. The prepared resin varnish is uniformly 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 the mixture is dried at 80 ° C to 110 ° C for 6 minutes to release. A photosensitive film with a support having a photosensitive resin composition layer on the mold PET was obtained.

The measurement method and the 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 produced in Examples and Comparative Examples was visually observed. In addition, when the photosensitive resin composition layer was cut out with a utility knife, the resin was scattered and cracks were observed. Further, the state of crack generation when the photosensitive film with a support was bent 180 ° was visually inspected and evaluated according to the following criteria.
〇: There is no repelling or unevenness, and no resin scattering or cracks can be seen.
X: Any of repellent, unevenness, resin scattering, and cracks can be seen.

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

(Measurement of average coefficient of linear thermal expansion)
The cured product for evaluation was cut into test pieces having a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed by a thermomechanical weighting method using a thermomechanical analyzer (Thermo Plus, TMA8310 manufactured by Rigaku Corporation). After the test piece was attached to the apparatus, measurements were made twice in succession under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. The average coefficient of linear thermal expansion (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 in which a copper layer with a thickness of 18 μm is patterned is formed is roughly treated with a surface treatment agent containing an organic acid (CZ8100, manufactured by MEC). I gave it a change. Next, the photosensitive resin composition layer of the photosensitive film with a support obtained in Examples and Comparative Examples was arranged so as to be in contact with the copper circuit surface, and a vacuum laminator (manufactured by Nikko Materials, VP160) was used. The copper-clad laminate, the photosensitive resin composition layer, and the support were laminated in this order to form a laminate. The crimping conditions were a vacuuming time of 30 seconds, a crimping temperature of 80 ° C., a crimping pressure of 0.7 MPa, and a pressurizing time of 30 seconds. The laminate was allowed to stand at room temperature for 30 minutes or more, and exposed to ultraviolet rays from the support of the laminate using a pattern forming apparatus using a round hole pattern. The exposure pattern is: 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 was used to draw a line and space of / 100 μm. After allowing to stand at room temperature for 30 minutes, the support was peeled off from the laminated body. A 1% by mass sodium carbonate aqueous solution at 30 ° C. was spray-developed on the entire surface of the photosensitive resin composition layer on the laminated plate at a spray pressure of 0.2 MPa for 2 minutes. After spray development, ultraviolet irradiation of 1 J / cm ² 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 an opening was formed on the laminate. .. This was used as an evaluation laminate.

(Evaluation of resolution)
The round holes patterned and formed on the evaluation laminate were observed by SEM (magnification 1000 times), and the minimum via diameter without residue and the minimum L / S without filling or peeling were measured. If there is no minimum L / S with no resin filling or peeling, it is marked with "x". The L / S shape was evaluated according to the following criteria.
◯: Observe the L / S at three points, and there is no peeling or filling between all the L / S.
X: Observe the L / S at three points, and resin burying or peeling is observed between any of the L / S.

(Evaluation of crack resistance)
The evaluation laminate was exposed to the air at −65 ° C. for 15 minutes, then heated at a heating rate of 180 ° C./min, then exposed to the atmosphere at 150 ° C. for 15 minutes, and then 180 ° C./min. A test was conducted in which the treatment by the heat cycle of lowering the temperature at the lowering rate of the above was repeated 500 times. 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 is observed.
X: Cracks and peeling are observed.

The abbreviations in the table are as follows.
(A) Ingredients-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 (nonvolatile content 70%)
(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
(C) Ingredients-Irgacure819: Bis (2,4,6-trimethylbenzoyl) -Phenylphosphine oxide (manufactured by BASF)
(D) Ingredients-NC3000H: Biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent about 272)
1031S: Tetrakis hydroxyphenylethane type epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 200)
(E) Ingredients-DPHA: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., acrylic equivalent: about 96)
Component (F) -EDGAc: Ethyldiglycolacetate-MEK: Methylethylketone-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 the average linear thermal expansion coefficient was low.

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

It has been confirmed that even when the components (E) to (F) are not contained in each of the examples, the same results as those of the above-mentioned examples are obtained, although the degree is different.

Claims (15)

(A) A resin containing an ethylenically unsaturated group and a carboxyl group,
(B) The average particle size (d50) is 0.5 μm or more and 2.5 μm or less, the particle size (D90) is 0.5 μm or more and 5.5 μm or less, and the specific surface area is 1.4 m ² / g or more and 10 m ² Inorganic filler less than / g,
(C) Photopolymerization initiator ,
( D) Epoxy resin and
(E) A photosensitive resin composition containing a reactive diluent .
The component (B) is surface-treated with a silane coupling agent and is surface-treated.
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.
The average particle size (d50) of the component (B) is a particle size at which the cumulative frequency of the volume-based particle size distribution obtained by the measurement by the laser diffraction / scattering type particle size distribution measuring device is 50%.
The particle size (D90) of the component (B) is a particle size at which the cumulative frequency of the volume-based particle size distribution obtained by the measurement by the laser diffraction / scattering type particle size distribution measuring device is 90%.
The specific surface area of the component (B) is the specific surface area obtained by measurement with a BET fully automatic specific surface area measuring device .
(E) A photosensitive resin composition containing dipentaerythritol hexaacrylate as a component . The first aspect of claim 1, wherein the average linear thermal expansion coefficient of the cured product obtained by photo-curing the photosensitive resin composition at 190 ° C. for 90 minutes at 25 ° C. to 150 ° C. is 10 ppm or more and 45 ppm or less. Photosensitive resin composition. The photosensitive resin composition according to claim 1 or 2, wherein the component (A) has a naphthalene skeleton. The photosensitive resin composition according to any one of claims 1 to 3, wherein the 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 the component (D) contains at least one of a biphenyl type epoxy resin and a tetraphenyl ethane type epoxy resin. The photosensitive resin composition according to any one of claims 1 to 5, wherein the specific surface area of the component (B) is 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 item according to any one of claims 1 to 7, wherein the content of the 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. Photosensitive resin composition. The content of the 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 according to the above. The item according to any one of claims 1 to 9, wherein the content of the 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. 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 having a support and a photosensitive resin composition layer provided on the support and containing the photosensitive resin composition according to any one of claims 1 to 10. A printed wiring board including an insulating layer formed of a cured product of the photosensitive resin composition according to any one of claims 1 to 10. The printed wiring board according to claim 13, wherein the insulating layer is a solder resist. A semiconductor device comprising the printed wiring board according to claim 13 or 14.