TWI776864B - Photosensitive resin composition - Google Patents

Abstract

The present invention provides a photosensitive resin composition and the like which can obtain a cured product having a high glass transition temperature and excellent undercut resistance and crack resistance, and which is excellent in resolution. The photosensitive resin composition of the present invention contains (A) a resin containing a naphthalene skeleton, an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler with an average particle diameter of 0.5 μm or more and 2.5 μm or less, (C) an acyl group Phosphine oxide-based photopolymerization initiator or oxime ester-based photopolymerization initiator, and (D) epoxy resin, the content of (B) component is when the total solid content of the photosensitive resin composition is 100% by mass , is 60 mass % or more and 85 mass % or less.

Description

Photosensitive resin composition

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

In a printed wiring board, a solder resist is sometimes provided as a permanent protective film for suppressing the adhesion of solder to unnecessary parts and for suppressing corrosion of the circuit board. As a solder resist, for example, the photosensitive resin composition described in Patent Document 1 is generally used. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-115672

Photosensitive resin compositions for solder resists generally require resolution, insulation, solder heat resistance, gold plating resistance, humidity and heat resistance, crack resistance (TCT resistance), and ultra-accelerated high temperature and humidity life test ( HAST) HAST resistance. In recent years, in response to the increase in density of printed wiring boards, workability or higher performance is also required for solder resist. In particular, the requirements for crack resistance are increasing year by year, and it is important to have more durability.

In addition, the solder resist is required to have a fine opening pattern to expose a part of the conductor layer having the wiring pattern in order to apply solder between the substrates and connect them. From the viewpoint of solder adhesion, the opening shape of the opening is required not to be inverted tapered. shape. Here, the so-called inverted tapered opening shape means a shape in which the opening is deeper and wider. In the present application, the property that such an opening shape does not easily become an inverted tapered shape is sometimes referred to as "undercut resistance".

An object of the present invention is to provide a photosensitive resin composition which is excellent in resolution and can obtain a cured product having a low average linear thermal expansion coefficient, a high glass transition temperature, and excellent undercut resistance and crack resistance; Photosensitive film, photosensitive film with support, printed wiring board and semiconductor device.

In general, if the inorganic filler with a large average particle size is contained in a large amount, the resolution is poor due to light reflection. Therefore, conventional photosensitive resin compositions contain many inorganic fillers with an average particle diameter of less than 0.5 μm. However, the inventors of the present invention have found that by containing both the specific (A) component and the specific photopolymerization initiator component in the photosensitive resin composition, when the average particle diameter is 0.5 μm or more and 2.5 μm or less, even if the photosensitive resin composition contains a large amount of An inorganic filler having a larger average particle diameter than the conventionally used inorganic filler can suppress light reflection, improve resolution, and the like, thereby completing the present invention.

That is, the present invention includes the following.

[1] A photosensitive resin composition comprising (A) a resin containing a naphthalene skeleton, 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, (C) ) acylphosphine oxide-based photopolymerization initiator or oxime ester-based photopolymerization initiator, and (D) epoxy resin, the content of (B) component is based on the total solid content of the photosensitive resin composition being 100 In mass %, it is 60 mass % or more and 85 mass % or less.

[2] The photosensitive resin composition according to [1], wherein the component (C) is bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, 2,4,6-trimethylbenzyl Any one of methylbenzyl-diphenyl-phosphine oxide and 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzyl oxime)].

[3] The photosensitive resin composition according to [1] or [2], wherein the component (A) contains an epoxy (meth)acrylate containing an acid-modified naphthalene skeleton.

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the component (D) contains at least any one of a biphenyl-type epoxy resin and a tetraphenylethane-type epoxy resin .

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the component (B) contains silicon oxide.

[6] A photosensitive film comprising the photosensitive resin composition according to any one of [1] to [5].

[7] A photosensitive film with a support having a support and The photosensitive resin composition layer containing the photosensitive resin composition as described in any one of [1]-[5] provided on this support body.

[8] 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 [5].

[9] The printed wiring board according to [8], wherein the insulating layer is a solder resist.

[10] A semiconductor device comprising the printed wiring board according to [8] or [9].

According to the present invention, it is possible to provide a photosensitive resin composition which can obtain a cured product with high glass transition temperature, excellent undercut resistance and excellent crack resistance and excellent resolution; a photosensitive film obtained by using the photosensitive resin composition, Photosensitive films, printed wiring boards, and semiconductor devices of supports.

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 contains (A) a resin containing a naphthalene skeleton, an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler with an average particle diameter of 0.5 μm or more and 2.5 μm or less, (C) an acyl group Phosphine oxide-based photopolymerization initiator Or the oxime ester-based photopolymerization initiator, and the photosensitive resin composition of (D) epoxy resin, and the content of (B) component, when the total solid content of the photosensitive resin composition is 100% by mass, It is 60 mass % or more and 85 mass % or less.

As described above, conventionally, many inorganic fillers having an average particle diameter of less than 0.5 μm are contained in the photosensitive resin composition. However, in the present invention, since the photosensitive resin composition contains both the (A) component and the (C) component, even if a large number of inorganic fillers having a larger average particle diameter than the conventionally used inorganic fillers are used, it is still possible to As a result of suppressing light reflection and improving resolution, it is possible to provide a photosensitive resin composition that can obtain a cured product having a high glass transition temperature and excellent undercut resistance and crack resistance.

The resin composition may further contain (E) a reactive diluent and (F) an organic solvent as needed. Hereinafter, each component contained in the photosensitive resin composition will be described in detail.

<(A) Resin containing naphthalene skeleton, ethylenically unsaturated group and carboxyl group>

The photosensitive resin composition contains (A) a resin containing a naphthalene skeleton, an ethylenically unsaturated group, and a carboxyl group. Since the component (A) is contained in the photosensitive resin composition together with the component (C) described later, even if the component (B) described later is used, light reflection can be suppressed and resolution can be improved. As a result, it is possible to provide A photosensitive resin composition having a high glass transition temperature, excellent undercut resistance and excellent crack resistance and excellent resolution of a cured product can be obtained.

Examples of ethylenically unsaturated groups include vinyl, allyl, propynyl, butenyl, ethynyl, phenylethynyl, maleic The amino group, the naphthalimide group, and the (meth)acryloyl group are preferably (meth)acryloyl groups from the viewpoint of the reactivity of the photoradical polymerization. The "(meth)acryloyl group" refers to a methacryloyl group and an acryl group.

The component (A) is not particularly limited as long as it is a resin containing a naphthalene skeleton, an ethylenically unsaturated group and a carboxyl group, which can undergo photo-radical polymerization and can be developed with alkali, but preferably has a naphthalene skeleton in one molecule. , carboxyl group and resin with two or more ethylenically unsaturated groups. When the naphthalene skeleton is contained, the rigidity of the molecules is increased, so that the molecular movement is suppressed. As a result, the glass transition temperature of the cured product is increased, and the average linear thermal expansion coefficient of the cured product is further lowered.

As one aspect of the component (A), for example, a naphthalene-type epoxy compound having a naphthalene skeleton (a naphthalene skeleton-containing epoxy compound) is reacted with an unsaturated carboxylic acid, and further reacted with an acid anhydride, which is obtained by reacting with an acid-modified epoxy compound. Epoxy ester resin of saturated naphthalene skeleton, etc. Specifically, an epoxy compound containing a naphthalene skeleton is reacted with an unsaturated carboxylic acid to obtain an epoxy ester resin containing an unsaturated naphthalene skeleton, and by reacting the epoxy ester resin containing an unsaturated naphthalene skeleton with an acid anhydride, the obtained Epoxy ester resin containing acid-modified unsaturated naphthalene skeleton.

The epoxy compound containing a naphthalene skeleton can be used as long as it has two or more epoxy groups in the molecule, and specific examples include dihydroxynaphthalene type epoxy resin, polyhydroxybinaphthalene type epoxy resin, polyhydroxynaphthalene type epoxy resin, and polyhydroxynaphthalene type epoxy resin. Naphthalene-type epoxy resins, such as naphthalene-type epoxy resins, binaphthol-type epoxy resins, and the like obtained by condensation reaction with aldehydes, have naphthalene-type epoxy resins having a naphthalene skeleton in the molecule. Any of these may be used alone, or two or more may be used in combination.

As a dihydroxynaphthalene type epoxy resin, for example, 1,3-diglycidoxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyl Glyceroxynaphthalene, 1,6-diglycidoxynaphthalene, 2,3-diglycidoxynaphthalene, 2,6-diglycidoxynaphthalene, 2,7-diglycidoxynaphthalene, and the like.

Examples of polyhydroxy binaphthyl-type epoxy resins include, for example, 1,1'-bis(2-glycidyloxy)naphthalene, 1-(2,7-diglycidyloxy)-1'-(2'-glycidyl) glyceryloxy)binaphthyl, 1,1'-bis(2,7-diglycidyloxy)naphthalene, and the like.

Examples of naphthalene-type epoxy resins obtained by condensation reaction of polyhydroxynaphthalene and aldehydes include 1,1'-bis(2,7-diglycidyloxynaphthyl)methane, 1-(2,7- Diglycidoxynaphthyl)-1'-(2'-glycidoxynaphthyl)methane, 1,1'-bis(2-glycidoxynaphthyl)methane.

Among these, polyhydroxy binaphthyl-type epoxy resins having two or more naphthalene skeletons in one molecule, and naphthalene-type epoxy resins obtained by condensation reaction of polyhydroxynaphthalene and aldehydes, are particularly preferred 1,1'-bis(2,7-diglycidyloxynaphthyl)methane, 1-(2,7-diglycidyloxynaphthyl)-1'-(2' with 3 or more epoxy groups -Glycidoxynaphthyl)methane, 1-(2,7-diglycidyloxy)-1'-(2'-glycidyloxy)binaphthyl, 1,1'-bis(2,7- Diglycidyloxy)naphthalene is preferable because it is excellent in heat resistance in addition to the average linear thermal expansion coefficient.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, cinnamic acid, and crotonic acid, and these may be used alone or in combination of two or more. Among them, from the viewpoint of improving the photocurability of the photosensitive resin composition, acrylic acid and methacrylic acid are preferred. In this specification, the naphthalene-type epoxy compound ester resin of the reaction product of the above-mentioned naphthalene-type epoxy compound and (meth)acrylic acid may be described as "naphthalene-type epoxy compound (meth)propylene" alkenoate", where the epoxy group of the naphthalene-type epoxy compound can be substantially eliminated by the reaction with (meth)acrylic acid. The term "(meth)acrylate" means methacrylate and acrylate. Acrylic acid and methacrylic acid are sometimes collectively referred to as "(meth)acrylic acid".

As the acid anhydride, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, diphenyl As for the ketone tetracarboxylic dianhydride and the like, any one of these may be used alone, or two or more of them may be used in combination. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferred from the viewpoint of improving the resolution and insulation reliability of the cured product.

When obtaining an epoxy ester resin containing an acid-modified unsaturated naphthalene skeleton, the epoxy ester resin containing an unsaturated naphthalene skeleton can be obtained by reacting an unsaturated carboxylic acid with an epoxy compound containing a naphthalene skeleton in the presence of a catalyst. Epoxy ester resin containing unsaturated naphthalene skeleton reacts with acid anhydride.

The amount of the catalyst used in this case is preferably in the range of 2 mass % or less, more preferably in the range of 0.0005 mass % to 1 mass %, based on the total mass of the unsaturated carboxylic acid, the naphthalene skeleton-containing epoxy compound, and the acid anhydride. More preferably, it is the range of 0.001 mass % - 0.5 mass %. Examples of catalysts include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7(DBU), 1,5-diazabicyclo[4.3.0 ]nonene-5(DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, Monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-amine Various amine compounds such as ethyl)aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide, etc.; phosphines such as trimethylphosphine, tributylphosphine, triphenylphosphine, etc.; tetramethyl phosphine Phosphonium salts such as phosphonium salts, tetraethylphosphonium salts, tetrapropylphosphonium salts, tetrabutylphosphonium salts, trimethyl(2-hydroxypropyl)phosphonium salts, triphenylphosphonium salts, benzylphosphonium salts, etc. , and phosphonium salts with chloride, bromide, carboxylate, hydroxide, etc. as representative counter anions; Or perylene salts such as phenyldimethyl perionate, and permalate salts with carboxylate, hydroxide, etc. as representative counter anions; such as phosphoric acid, p-toluenesulfonic acid, acid compounds of sulfuric acid, etc. The reaction can be carried out in the range of 50°C to 150°C, preferably in the range of 80°C to 120°C.

When obtaining the epoxy ester resin containing an acid-modified unsaturated naphthalene skeleton, an organic solvent can also be used. As an organic solvent, the same organic solvent as (F) organic solvent mentioned later can be used.

When obtaining an epoxy ester resin containing an acid-modified unsaturated naphthalene skeleton, a polymerization inhibitor such as hydroquinone can also be used. The amount of the polymerization inhibitor used in this case is preferably 2 mass % or less, more preferably 0.0005 mass % to 1 mass %, based on the total mass of the unsaturated carboxylic acid, the naphthalene skeleton-containing epoxy compound, and the acid anhydride. , and more preferably in the range of 0.001 mass % to 0.5 mass %.

As the epoxy ester resin containing an acid-modified unsaturated naphthalene skeleton, an epoxy (meth)acrylate containing an acid-modified naphthalene skeleton is preferred. The so-called epoxy ester resin containing an acid-modified unsaturated naphthalene skeleton refers to an epoxy ester containing an acid-modified unsaturated naphthalene skeleton obtained by using an epoxy compound containing a naphthalene skeleton and using (meth)acrylic acid as an unsaturated carboxylic acid resin.

As another aspect of the component (A), for example, a (meth)acrylic resin having a structural unit obtained by polymerizing (meth)acrylic acid is reacted with an epoxy compound containing an ethylenically unsaturated group and a naphthalene skeleton, and ethylene is introduced. A (meth)acrylic resin containing an unsaturated modified naphthalene skeleton containing an unsaturated group. Furthermore, the hydroxyl group generated when the unsaturated group is introduced may also react with the acid anhydride. As an acid anhydride, the same thing as the above-mentioned acid anhydride can be used, and the preferable range is also the same.

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

As the acid value of the component (A), from the viewpoint of improving the alkali developability of the photosensitive resin composition, the acid value is preferably 0.1 mgKOH/g or more, more preferably 0.5 mgKOH/g or more, still more preferably 1 mgKOH/g g or more. In addition, from the viewpoint of suppressing elution of the fine pattern of the cured product by development and improving insulation reliability, the acid value is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, and still more preferably 100 mgKOH/g or less. Here, the residual acid value of the carboxyl group present in the so-called acid value system (A) component can be measured by the following method. First, after about 1 g of the resin solution measured by the fine weighing, 30 g of acetone was added to the resin solution to dissolve the resin solution uniformly. Next, an appropriate amount of indicator phenolphthalein was added to the solution, and titration was performed using a 0.1N KOH aqueous solution. Next, the acid value was calculated from 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 of KOH (mL), Wp represents the measurement of the resin solution mass (g), and I represents the non-volatile matter ratio (mass %) of the measurement resin solution .

From the viewpoint of storage stability, in the production of the component (A), the ratio of the molar number of epoxy groups of the naphthalene-type epoxy resin to the total number of carboxyl molar groups of the unsaturated carboxylic acid and acid anhydride is preferably 1:0.8 to 1:0. The range of 1.3 is more preferably the range of 1:0.9 to 1.2.

From the viewpoint of improving alkali developability, the content of the component (A) is preferably 5% by mass or more, more preferably 8% by mass or more, when the total solid content of the photosensitive resin composition is 100% by mass, and More preferably, it is 10 mass % or more. From the viewpoint of improving heat resistance, the upper limit is preferably at most 35% by mass, more preferably at most 30% by mass, and still more preferably at most 25% by mass.

<(B) Inorganic filler having an average particle diameter of 0.5 μm or more and 2.5 μm or less> The photosensitive resin composition contains (B) an inorganic filler having an average particle diameter of 0.5 μm or more and 2.5 μm or less. By containing (B) component, the photosensitive resin composition which can obtain the hardened|cured material with a low average linear thermal expansion coefficient can be provided.

The material of the inorganic filler is not particularly limited, but examples include silicon oxide, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite , Boehmite, aluminum hydroxide, 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, etc. Among these, silicon oxide is particularly suitable. In addition, the silicon oxide is preferably spherical silicon oxide. The inorganic filler may be used alone or in combination of two or more.

The average particle size of the inorganic filler is necessary to contain a large amount of the inorganic filler in order to obtain a cured product with a low average linear thermal expansion coefficient, and from the viewpoint of its fillability, it is preferably 0.5 μm or more, more preferably 0.8 μm or more, and still more. Preferably it is 1 micrometer or more. From the viewpoint of obtaining excellent resolution, the upper limit of the average particle diameter is preferably 2.5 μm or less, more preferably 2 μm or less, still more preferably 1.5 μm or less, and even more preferably 1.3 μm or less. Examples of commercially available inorganic fillers having such an average particle size include "SC4050" and "Admafine" manufactured by Admatechs, "SFP series" manufactured by Denki Chemical Industries, and "SP (SP)" manufactured by Nippon Steel & Sumitomo Metal Materials. H) Series", "Sciqas Series" manufactured by Sakai Chemical Industry Co., Ltd., "Seahostar Series" manufactured by Nippon Shokubai Corporation, "AZ Series" and "AX Series" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd., "B Series" manufactured by Sakai Chemical Industry Co., Ltd. ", "BF series" and so on.

The average particle size of the inorganic filler can be based on the Mie scattering theory, and the laser diffraction can be used. measured by scattering method. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis using a laser diffraction particle size distribution analyzer, and the median diameter can be measured as an average particle size. As a measurement sample, what disperse|distributed the inorganic filler in water with an ultrasonic wave can be preferably used. As the laser diffraction particle size distribution analyzer, "LA-500" manufactured by Horiba Corporation, "SALD-2200" manufactured by Shimadzu Corporation, and the like can be used.

Inorganic fillers, from the viewpoint of improving moisture resistance and dispersibility, are preferably aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilane compounds, organic Treatment with one or more surface treatment agents such as silazane compounds and titanate-based coupling agents. Commercially available surface treatment agents include, for example, "KBM403" (3-glycidyloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. , "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-term) manufactured by Shin-Etsu Chemical Co., Ltd. chain epoxy silane coupling agent), etc.

The content of the inorganic filler is preferably 60% by mass or more, more preferably 60.5% by mass, when the nonvolatile content in the photosensitive resin composition is 100% by mass, from the viewpoint of obtaining a cured product with a low average linear thermal expansion coefficient. More than that, more preferably, it is 61 mass % or more. From the viewpoint of suppressing light reflection, the upper limit is preferably 85% by mass or less, more preferably 82% by mass or less, and still more preferably 80% by mass or less.

<(C) Acylphosphine oxide-based photopolymerization initiator or oxime ester-based photopolymerization initiator>

The photosensitive resin composition contains (C) an acylphosphine oxide-based photopolymerization initiator or an oxime ester-based photopolymerization initiator. Since the photosensitive resin composition contains the (C) component together with the (A) component, even if the (B) component having a large average particle size is used, the points, the light reflection can still be suppressed. As a result, it is possible to provide a photosensitive resin composition that has a high glass transition temperature, and that can obtain a cured product having excellent undercut resistance and crack resistance.

The acylphosphine oxide-based photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator having an acylphosphine oxide group. Specific examples of the acylphosphine oxide-based photopolymerization initiator include bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide), 2,4,6-trimethylbenzene Carboxylic-diphenyl-phosphine oxide. Examples of commercially available acylphosphine oxide-based photopolymerization initiators include, for example, "IRGACURE TPO" and "IRGACURE 819" manufactured by BASF Corporation.

The oxime ester-based photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator having an oxime ester group. Specific examples of oxime ester-based photopolymerization initiators include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) and the like. Examples of commercially available oxime ester-based photopolymerization initiators include, for example, "IRGACURE OXE01" and "IRGACURE OXE02" manufactured by BASF Corporation.

Among these, from the viewpoint of improving the resolution, the component (C) is preferably bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, 2,4,6-trimethyl Any of benzalyl-diphenyl-phosphine oxide and 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzyl oxime)]. (C)component may be used individually by 1 type, and may use 2 or more types together.

Furthermore, the photosensitive resin composition may contain N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl as a photopolymerization initiator in combination with (C) component tertiary amines such as esters, amyl 4-dimethylaminobenzoate, triethylamine, triethanolamine, etc., and may also contain pyrazolines, anthracenes, coumarins, xanthones, sulfur Photosensitizers such as xanthones. These may be used individually by 1 type, and may use 2 or more types together.

The content of the component (C) is preferably 0.01 mass % or more when the total solid content of the photosensitive resin composition is 100 mass % from the viewpoint of sufficiently photocuring the photosensitive resin composition and improving insulation reliability. , more preferably 0.03 mass % or more, still more preferably 0.05 mass % or more. On the other hand, in order to suppress the decrease in resolution due to excessive sensitivity, the upper limit is preferably 2 mass % or less, more preferably 1.5 mass % or less, and still more preferably 1 mass % or less.

<(D) Epoxy resin> The photosensitive resin composition contains (D) epoxy resin. Insulation reliability can be improved by containing (D) component. However, (D)component does not contain the epoxy resin containing a naphthalene skeleton, an ethylenically unsaturated group, and a carboxyl group.

Examples of the component (D) include fluorine-containing epoxy resins such as bisphenol AF type epoxy resin and perfluoroalkyl type epoxy resin; bisphenol A type epoxy resin; bisphenol F type epoxy resin; Phenol S type epoxy resin; Bixylenol type epoxy resin; Dicyclopentadiene type epoxy resin; Trisphenol type epoxy resin; Naphthol novolac type epoxy resin; Phenol novolac type epoxy resin; Tertiary-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 epoxy resin; biphenyl epoxy resin; chain aliphatic epoxy resin; epoxy resin with butadiene structure; alicyclic epoxy resin, alicyclic epoxy resin with ester skeleton; Heterocyclic epoxy resin; epoxy resin containing spiro ring; cyclohexane dimethanol type epoxy resin; naphthyl ether type epoxy resin; trimethylol type epoxy resin; tetraphenylethane type epoxy resin , halogenated epoxy resins, and the like, from the viewpoint of improving adhesion, preferably bisphenol F-type epoxy resins, biphenyl-type epoxy resins, and more preferably biphenyl-type epoxy resins. Furthermore, from the viewpoint of improving heat resistance, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, naphthyl ether-type epoxy resins, and tetraphenylethane-type epoxy resins are preferable, and more Preferably it is a tetraphenylethane type epoxy resin. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types. From the viewpoint of improving adhesion and heat resistance, the component (D) preferably contains at least one of a biphenyl-type epoxy resin and a tetraphenylethane-type epoxy resin.

The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile content of the epoxy resin is 100% by mass, it is preferably at least 50% by mass or more of 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 epoxy resins include "HP4032", "HP4032D", "HP4032SS", "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation, "828US", "jER828EL" (double-type epoxy resin) manufactured by Mitsubishi Chemical Corporation Phenol A epoxy resin), "jER807" (bisphenol F epoxy resin), "jER152" (phenol novolac epoxy resin), "630", "630LSD" (glycidylamine epoxy resin) , "ZX1059" (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., "YD-8125G" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. type epoxy resin), "EX-721" (glycidyl ester type epoxy resin) manufactured by NAGASE CHEM TEX, "CELLOXIDE 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by DAICEL, "PB -3600" (alicyclic epoxy resin with a butadiene structure), "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical Co., Ltd., Mitsubishi Chemical Corporation "630LSD" (glycidylamine type epoxy resin) manufactured by DIC Corporation, "E-7432", "E-7632" (perfluoroalkyl type epoxy resin) manufactured by DAICEL Corporation, "HP-4700 manufactured by DIC Corporation" ", "HP-4710" (naphthalene type 4-functional epoxy resin), "N-690" (cresol novolac epoxy resin), "N-695" (cresol novolac epoxy resin), " HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin), "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Oxygen resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., "ESN485" "(naphthol novolac epoxy resin), "YSLV-80XY" (tetramethylbisphenol F epoxy resin), "YX4000H", "YL6121" (biphenyl epoxy resin) manufactured by Mitsubishi Chemical Corporation , "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "G-500" manufactured by Mitsubishi Chemical Corporation YL7800" (Fine-type epoxy resin), "1010" (solid bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation ), "1031S" (tetraphenylethane type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), etc.

The content of the component (D) is preferably 1 mass % or more when the total solid content of the photosensitive resin composition is 100 mass % from the viewpoint of obtaining an insulating layer exhibiting good tensile rupture strength and insulation reliability. , more preferably 5 mass % or more, still more preferably 8 mass % or more. The upper limit of the epoxy resin content is not particularly limited as long as the effects of the present invention can be 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 from 50 to 5000, more preferably from 50 to 3000, still more preferably from 80 to 2000, still more preferably from 110 to 1000. By making it into this range, the crosslinking density of the hardened|cured material of the photosensitive resin composition becomes sufficient, and an insulating layer with small surface roughness can be obtained. In addition, the epoxy equivalent can be measured based on JIS K7236, and it is the resin mass containing 1 equivalent of epoxy groups.

The weight average molecular weight of the epoxy resin is preferably from 100 to 5000, more preferably from 250 to 3000, still more preferably from 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 gel permeation chromatography (GPC).

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

Typical photosensitive (meth)acrylate compounds include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, ethylene glycol, methoxytetraethylene glycol, Mono- or diacrylates of glycols such as polyethylene glycol and propylene glycol, acrylamides such as N,N-dimethylacrylamide and N-methylol acrylamide, N,N-diacrylates of acrylic acid Aminoalkyl acrylates such as methylaminoethyl ester, polyols such as trimethylolpropane, pentaerythritol, dipentaerythritol, etc. or their ethylene oxide adducts, propylene oxide adducts or ε- Polyvalent acrylates of adducts of caprolactone, phenols such as phenoxyacrylate, phenoxyethyl acrylate, or acrylates such as ethylene oxide adducts or propylene oxide adducts , epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether, melamine acrylates, and/or methacrylates corresponding to the above acrylates, etc. Among them, polyacrylates or polymethacrylates are preferred, and examples of trimethylacrylates or methacrylates include trimethylolpropane tri(meth)acrylate and pentaerythritol triacrylate. (Meth)acrylate, trimethylolpropane EO addition tri (meth)acrylate, glycerol PO addition tri (meth)acrylate, pentaerythritol tetra (meth)acrylate, tetrahydrofurfuryl alcohol oligo ( meth)acrylate, ethylcarbitol oligo(meth)acrylate, 1,4-butanediol oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate ester, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, N ,N,N',N'-(meth)acrylate of tetrakis(β-hydroxyethyl)ethylenediamine, etc. As acrylates or methacrylates of 3 or more valence, tris(2 -(Meth)acryloyloxyethyl)phosphate, tris(2-(meth)acryloyloxypropyl)phosphate, tris(3-(meth)acryloyloxypropyl)phosphate , tris(3-(meth)acryloyl-2-hydroxyoxypropyl) phosphate, bis(3-(meth)acryloyl-2-hydroxyoxypropyl)(2-(methyl) ) Acryloyloxyethyl)phosphate, (3-(meth)acryloyl-2-hydroxyoxypropyl)bis(2-(meth)acrylooxyethyl)phosphate, etc. Triester (meth)acrylate. Any of these photosensitive (meth)acrylate compounds may be used alone, or two or more of them may be used in combination.

The content at the time of preparing the component (E) is preferably from 1 mass % to 100 mass % of the total solid content of the photosensitive resin composition from the viewpoint of promoting photocuring and suppressing stickiness when a cured product is prepared. 10% by mass, more preferably 3% by mass to 8% by mass.

<(F) Organic solvent> The photosensitive resin composition may further contain (F) an organic solvent. The viscosity of the varnish can be adjusted by containing the component (F). Examples of the organic solvent (F) include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl cellulose, etc. Glycol ethers such as base carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc., ethyl acetate, butyl acetate, butyl cellosolve Esters of acetate, carbitol acetate, ethyl diethylene glycol, etc., aliphatic hydrocarbons such as octane and decane, petroleum ether, petroleum naphtha, hydrogenated naphtha, solvent naphtha, etc. solvent, etc. These can be used alone or in combination of two or more. The content in the case of using the organic solvent can be appropriately adjusted from the viewpoint of coatability of the photosensitive resin composition.

<(G) Other additives> The photosensitive resin composition may further contain (G) other additives to the extent that the object of the present invention is not impaired. As (G) other additives can be added such as thermoplastic resins, organic fillers, fine particles of melamine, organic bentonite, etc., phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc. Coloring agent of hydroquinone, phenanthiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, biphloroglucinol, etc., polymerization inhibitor, Benton, montmorillonite, etc. tackifier, polysiloxane Defoamer of fluorine-based, vinyl resin-based, brominated epoxy compounds, oxygen-modified brominated epoxy compounds, antimony compounds, phosphorus-based compounds, aromatic condensed phosphoric acid esters, halogen-containing condensed phosphoric acid esters, etc. Various additives such as thermosetting resins such as phenol-based hardeners, cyanate-based hardeners, etc.

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

<Physical properties and applications of the photosensitive resin composition> Even if the photosensitive resin composition of the present invention uses a large amount of the (B) component with a large average particle diameter, since it contains the (A) component and the (C) component, it exhibits excellent resolution. characteristics. Therefore, residues, such as resin, do not exist in an unexposed part. In addition, since resolution is excellent, resin is usually not embedded or peeling is not present between L/S (line/space). The minimum opening diameter without residue is preferably 100 μm or less, more preferably 90 μm or less, and still more preferably 80 μm or less. The lower limit is not particularly limited, and may be 1 μm or more or the like. The evaluation of the resolution can be performed according to the method described in the below-mentioned <Evaluation of the resolution, crack resistance, and undercut resistance>.

After photocuring, the photosensitive resin composition of the present invention is thermally cured at 190° C. for 90 minutes, and the cured product exhibits a low average linear thermal expansion coefficient. 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 at most 45 ppm, more preferably at most 40 ppm, still more preferably at most 36 ppm, and more preferably at most 35 ppm. The lower limit is not particularly limited, and may be 10 ppm or more. The measurement of the average coefficient of linear thermal expansion can be carried out according to the method described in the below-mentioned <Measurement of the average coefficient of linear thermal expansion and glass transition temperature>.

After photocuring, the photosensitive resin composition of the present invention is thermally cured at 190° C. for 90 minutes, and the cured product exhibits a high glass transition temperature. That is, an insulating layer and a solder resist having a high glass transition temperature are obtained. The glass transition temperature is preferably 160°C or higher, more preferably 170°C or higher, and still more preferably 180°C or higher. The upper limit is not particularly limited, and may be 300° C. or lower. The glass transition temperature can be measured according to the method described in <Measurement of Average Linear Thermal Expansion and Glass Transition Temperature> described later.

After photocuring, the photosensitive resin composition of the present invention exhibits a characteristic of being excellent in undercut resistance after thermal curing at 190° C. for 90 minutes. That is, an insulating layer and a solder resist excellent in undercut resistance are obtained. The undercut is preferably at most 5 μm, more preferably at most 4 μm, and still more preferably at most 3 μm. The lower limit is not particularly limited, and may be 0.1 μm or more. The undercut can be measured according to the method described in the below-mentioned <Evaluation of resolution, crack resistance, and undercut resistance>.

After photocuring, the photosensitive resin composition of this invention shows the characteristic which is excellent in crack resistance of the hardened|cured material after thermal hardening at 190 degreeC for 90 minutes. That is, an insulating layer and a solder resist excellent in crack resistance are obtained. Even if the temperature rise test between -65°C and 150°C was performed 500 times, no cracks and peeling were seen. The evaluation of crack resistance can be performed according to the method described in <Evaluation of resolution, crack resistance, and undercut resistance> mentioned later.

The application of the photosensitive resin composition of the present invention is not particularly limited, and can be used for photosensitive films, photosensitive films with supports, insulating resin sheets such as prepregs, circuit boards (for laminates, multilayer printed wiring boards) Applications, etc.), solder resists, underfills, die bonding materials, semiconductor sealing materials, buried hole resins, parts embedding resins, etc., are used in a wide range of applications that require photosensitive resin compositions. Among them, photosensitive resin compositions for insulating layers of printed wiring boards (printed wiring boards using cured products of photosensitive resin compositions as insulating layers), photosensitive resin compositions for interlayer insulating layers (with The cured product of the photosensitive resin composition is a printed wiring board with an interlayer insulating layer), a photosensitive resin composition for plating formation (a printed wiring board with plating formed on the cured product of the photosensitive resin composition), and a solder resist Photosensitive resin composition (printed wiring board using the cured product of the photosensitive resin composition as a solder resist).

[Photosensitive film] The photosensitive resin composition of the present invention can be coated on a support substrate in the state of a resin varnish, dried with an organic solvent to form a photosensitive resin composition layer, and can be made into a photosensitive film. Moreover, the photosensitive thin film previously formed on the support body can also be used by laminating|stacking on a support substrate. The photosensitive film can be laminated on various support substrates. Examples of the supporting substrate include substrates such as glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like.

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

Examples of the support include polyethylene terephthalate films, polyethylene naphthalate films, polypropylene films, polyethylene films, polyvinyl alcohol films, polyacetate films, and the like, particularly preferably polyethylene terephthalate films. Ethylene terephthalate film.

Examples of commercially available supports include "Alphand MA-410" and "E-200C" manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and "PS-25" manufactured by Teijin Corporation. PS series such as polyethylene terephthalate, etc., but not limited to these. In order to facilitate the removal of the photosensitive resin composition layer, these supports are preferably coated with a release agent such as a polysiloxane coating agent. 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 be 5 μm or more, cracking of the support at the time of peeling of the support before image development can be suppressed, and by setting the thickness to 50 μm or less, the resolution at the time of exposure from the support can be improved. Moreover, it is preferable that it is a support body with a low fish-eye. The fish-eye here refers to the entry of foreign matter, undissolved matter, oxidatively degraded matter, etc. of the material into the film when the material is produced by thermal fusion, kneading, extrusion, biaxial stretching, expansion method, or the like.

Moreover, in order to reduce the light scattering at the time of exposure with active energy rays, such as an ultraviolet-ray, it is preferable that a support body is excellent in transparency. Specifically, it is preferable that the turbidity (the turbidity standardized by JIS K6714) serving as an index of transparency is 0.1 to 5 for the support. Furthermore, the photosensitive resin composition layer is protected with a protective film.

The photosensitive resin composition layer side of the photosensitive film with the support is protected by a protective film to prevent adhesion or scratches such as dirt on the surface of the photosensitive resin composition layer. 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 still more preferably in the range of 10 μm to 30 μm. By setting the thickness to be 1 μm or more, the handling properties of the protective film can be improved, and by setting the thickness to 40 μm or less, the low cost tends to be improved. Moreover, as for the protective film, it is preferable that the adhesive force between the photosensitive resin composition layer and the protective film is smaller with respect to the adhesive force between the photosensitive resin composition layer and the support.

The photosensitive film with a support of the present invention can be prepared by, for example, preparing a resin varnish prepared by dissolving the photosensitive resin composition of the present invention in an organic solvent according to a method known to the industry, and coating the resin varnish on the support. It is manufactured by drying an organic solvent by heating, a hot air blow, etc., and forming a photosensitive resin composition layer. Specifically, first, after the air bubbles in the photosensitive resin composition are completely removed by a vacuum defoaming method, etc., the photosensitive resin composition is coated on the support, and the solvent is removed by a hot air furnace or a far-infrared furnace and dried. Then, as required, a protective film is laminated on the obtained photosensitive resin composition layer to manufacture a photosensitive film with a support. The specific drying conditions vary depending on the curability of the photosensitive resin composition or the amount of organic solvent in the resin varnish, but for resin varnishes containing 30% by mass to 60% by mass of organic solvent, drying can be performed at 80°C to 120°C 3 minutes to 13 minutes. The amount of the organic solvent remaining in the photosensitive resin composition layer is preferably 5 mass % or less, more preferably 2 mass % or less, based on the total amount of the photosensitive resin composition layer, from the viewpoint of preventing diffusion of the organic solvent in the subsequent steps. Those skilled in the art can set appropriate and preferred drying conditions through simple experiments. The thickness of the photosensitive resin composition layer is preferably in the range of 5 μm to 500 μm, more preferably in the range of 10 μm to 200 μm, from the viewpoint of improving the handleability and suppressing the decrease in sensitivity and resolution inside the photosensitive resin composition layer. More preferably, it is the range of 15-150 micrometers, More preferably, it is the range of 20-100 micrometers, Most preferably, it is the range of 20-60 micrometers.

Examples of coating methods for the photosensitive resin composition include gravure coating, microgravure coating, reverse coating, extrusion coating, die coating, slot die coating, and lip die coating. Cloth method, notch wheel coating method, blade coating method, roll coating method, blade coating method, curtain flow coating method, chamber gravure coating method, slit orifice method, spray coating method, Dip coating method, etc. The photosensitive resin composition can be applied several times or once, and can also be applied by combining several different methods. Among them, the die coating method excellent in uniform coating properties is preferred. In addition, in order to avoid the contamination of foreign matter, etc., it is preferable to carry out the coating step in an environment such as a clean room where foreign matter generation is less.

[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 produced using the above-mentioned photosensitive film or photosensitive film with a support. The following describes the case where the insulating layer is solder resist.

<Coating and drying step> The photosensitive resin composition is directly coated on 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 substrate include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. In addition, a circuit board here means the board|substrate which formed the conductor layer (circuit) after patterning on the single side|surface or both sides of the board|substrate as mentioned above. In addition, in the multilayer printed wiring board in which the conductor layer and the insulating layer are laminated with each other, the substrate of the conductor layer (circuit) which is patterned on one or both sides of the outermost layer of the multilayer printed wiring board is also included here. It is called the circuit board. In addition, the surface of the conductor layer may be subjected to roughening treatment in advance by blackening treatment, copper etching, or the like.

As a coating method, generally, full-surface printing by a screen printing method is often used, but any method other than that can be used as long as it is a coating method that can be uniformly coated. For example, spray coating method, hot melt coating method, bar coating method, applicator method, blade coating method, blade coating method, air knife coating method, curtain coating method, roll coating method , Gravure coating method, flexographic printing method, dip coating method, brush coating method, and other common coating methods can be used. After coating, it is dried with a hot-air oven or a far-infrared oven as needed. The drying conditions are drying at 80°C to 120°C for 3 minutes to 13 minutes. In this way, the photosensitive thin film is formed on the circuit board.

<Lamination step> In addition, when the 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 lamination step, when the photosensitive film with the support has a protective film, after the protective film is removed, the photosensitive film with the support and the circuit substrate are preheated as required, and the photosensitive resin is formed by pressing and heating. The side of the material layer is pressed against the circuit substrate. In the photosensitive film with a support, the method of laminating|stacking on a circuit board under reduced pressure by a vacuum lamination method can be used suitably.

The conditions of the lamination step are not particularly limited. For example, the pressing temperature (lamination temperature) is preferably set to 70°C to 140°C, and the pressing 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 pressing time is preferably 5 seconds to 300 seconds, and the air pressure is laminated under a reduced pressure of 20 mmHg (26.7 hPa) or less. In addition, a batch type may be used for a lamination process, and the continuous type using a roll may be sufficient as it. The vacuum lamination method can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum coater manufactured by NIKKO MATERIALS Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., a dry roll coater manufactured by Hitachi Kogyo Co., Ltd., and a product manufactured by Hitachi AIC Co., Ltd. can be exemplified. Vacuum laminator, etc. In this way, the photosensitive resin composition layer is formed on the circuit board.

<Exposure step> After the photosensitive film (photosensitive resin composition layer) is provided on the circuit board by the coating and drying step or the lamination step, the photosensitive resin composition layer is then passed through a mask pattern. The exposure step of irradiating a specific part with actinic light to photoharden the photosensitive resin composition layer of the irradiated part. Examples of active rays include ultraviolet rays, visible rays, electron beams, X-rays, and the like, and ultraviolet rays are particularly preferred. The irradiation dose of ultraviolet rays is about 10mJ/cm ² to 1000mJ/cm ² . The exposure method includes a contact exposure method in which a mask pattern is adhered to a printed wiring board, and a non-contact exposure method in which the mask pattern is not adhered and exposed using parallel light, and either can be used. Moreover, when a support body exists on the photosensitive resin composition layer, exposure may be carried out from the support body, and exposure after peeling a support body may be sufficient.

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

<Development step> After the exposure step, when there is a support on the photosensitive resin composition layer, after removing the support, the part that has not been photohardened (unexposed) is removed by wet development or dry development. part) and by developing, a pattern can be formed.

In the case of the above-mentioned wet development, as the developer, an alkaline aqueous solution, water-based developer, organic solvent, etc., which are safe, stable and have good operability, are used, among which development using an alkaline aqueous solution is preferred. step. In addition, as the developing method, conventional methods such as spraying, shaking and dipping, brushing, and washing are suitably used.

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 hydrogencarbonates such as sodium carbonate and sodium hydrogencarbonate, sodium phosphate and phosphoric acid. Aqueous solutions of alkali metal phosphates such as potassium, sodium pyrophosphate, potassium pyrophosphate, and other alkali metal pyrophosphates, or aqueous solutions of organic bases such as tetraalkylammonium hydroxide that do not contain metal ions, preferably those that do not contain metal ions , From the viewpoint of not affecting the semiconductor wafer, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred. In these alkaline aqueous solutions, in order to improve the developing effect, surfactants, antifoaming agents, etc. can be added to the developing solution. The pH of the above-mentioned alkaline aqueous solution is, for example, preferably in the range of 8 to 12, more preferably in the range of 9 to 11. Moreover, it is preferable that the alkali concentration of the said alkaline aqueous solution is 0.1 mass % - 10 mass %. The temperature of the above-mentioned alkaline aqueous solution can be appropriately selected according to the resolution of the photosensitive resin composition layer, but is preferably 20°C to 50°C.

Examples of organic solvents used as the developer include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, and diethylene glycol monomethyl ether. , Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether.

The concentration of these organic solvents is preferably 2% by mass to 90% by mass with respect to the total amount of the developing solution. In addition, the temperature of these organic solvents can be adjusted according to the resolution. In addition, these organic solvents can be used individually or in combination of 2 or more types. Examples of the organic solvent-based developer used alone are, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isotope Butyl ketone, γ-butyrolactone.

In the pattern formation, if necessary, two or more of the above-mentioned developing methods may be used in combination. The developing methods include a dipping method, a liquid coating method, a spraying method, a high-pressure spraying method, a brushing method, a washing method, and the like, and the high-pressure spraying method is preferable because the resolution is improved. When the spraying method is used, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

<Thermal hardening (thermal baking) process> After the said image development process is complete|finished, the thermal hardening (thermal baking) process is performed, and a solder resist is formed. As the thermal baking step, an ultraviolet irradiation step using a high pressure mercury lamp or a heating step using a clean oven is exemplified. When irradiating the ultraviolet rays, the irradiation amount can be adjusted as necessary, for example, the irradiation amount can be about 0.05J/cm ² to 10J/cm ² . And the heating conditions can be appropriately selected according to the type and content of the resin components in the photosensitive resin composition, but it is preferably in the range of 150°C to 220°C for 20 minutes to 180 minutes, more preferably 160°C to 200°C for a duration of 20 minutes to 180 minutes. Choose from a range of 30 minutes to 120 minutes.

<Other steps> After the solder resist is formed on the printed wiring board, a punching step and a desmearing step may be further included. These steps can be carried out according to various methods known to those skilled in the art for the manufacture of printed wiring boards.

After the solder resist is formed, as desired, the solder resist formed on the circuit board is subjected to a punching step to form via holes and through holes. The punching step can be performed by conventional methods such as drill, laser, plasma, etc., and these methods can be combined as required, but it is preferably a punching step using a laser such as a carbon dioxide laser, a YAG laser, etc. .

The desmear step is a step of desmear treatment. Resin residues (smears) generally adhere to the inside of the openings formed in the punching step. Since this smear becomes the cause of poor electrical connection, the process of removing the smear (smear-removing process) is performed in this step.

Desmear treatment can be performed by dry de-smear treatment, wet de-smear treatment, or a combination thereof.

Examples of the dry desmear treatment include desmear treatment using plasma, for example. The desmear treatment using plasma can be performed using a commercially available plasma desmear treatment device. Among the commercially available plasma desmear treatment devices, the preferred examples for the manufacture of printed wiring boards are microwave plasma devices manufactured by Nissin Corporation, atmospheric pressure plasma etching devices manufactured by Sekisui Chemical Industry Co., Ltd., and the like.

Examples of the wet desmear treatment include desmear treatment using an oxidizing agent solution. When using the oxidizing agent solution for the desmear treatment, it is preferable to sequentially perform the swelling treatment with the swelling liquid, the oxidation treatment with the oxidizing agent solution, and the neutralization treatment with the neutralizing liquid. Examples of the swelling liquid include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by ATOTECH JAPAN, for example. The swelling treatment is preferably performed by immersing the substrate on which pinholes and the like are formed in a swelling liquid heated at 60° C. to 80° C. for 5 minutes to 10 minutes. The oxidant solution is preferably an aqueous alkaline permanganic acid solution, and examples thereof include a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous sodium hydroxide solution. The oxidation treatment of the oxidizing agent solution is preferably performed by immersing the substrate after the swelling treatment in the oxidizing agent solution heated to 60° C. to 80° C. for 10 minutes to 30 minutes. As a commercial item of the alkaline permanganic acid aqueous solution, "Concentrate Compact CP", "Doesing Solution Securiganth P" by ATOTECH JAPAN company, etc. are mentioned, for example. The neutralization treatment in the neutralization solution is preferably performed by immersing the substrate after the oxidation treatment in the neutralization solution at 30° C. to 50° C. for 3 minutes to 10 minutes. An acidic aqueous solution is preferable as a neutralization liquid, and "Reduction Solution Securiganth P" by ATOTECH JAPAN company is mentioned as a commercial item, for example.

When the dry desmear treatment and the wet desmear treatment are combined, 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 way as in the case of the solder resist, or after the thermal hardening step, the punching step, the desmearing step and the plating step can be carried out.

The plating step is a step of forming a conductor layer on the insulating layer. The conductor layer can be formed by combining electroless plating and electrolytic plating, and a plating resist with a pattern opposite to that of the conductor layer can also be formed, and the conductor layer can be formed only by electroless plating. As the subsequent pattern formation method, for example, a subtraction method, a semi-additive method, etc., which are known to those skilled in the art, can be used.

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

Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as locomotives, automobiles, trains, ships, and airplanes).

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 so-called "conduction part" refers to "the part in the printed wiring board that transmits electrical signals", and the place may be the surface or the embedded part. In addition, the semiconductor wafer is not particularly limited as long as it is an electrical circuit element made of a semiconductor material.

The mounting method of the semiconductor chip in the manufacture of the semiconductor device of the present invention is not particularly limited if it can effectively exert the function of the semiconductor chip, and specific examples include a wire bonding mounting method, a flip chip mounting method, and a bumpless build-up layer (BBUL) method. installation method, installation method using anisotropic conductive film (ACF), installation method using non-conductive film (NCF), etc. Here, the so-called "mounting method using bumpless build-up layer (BBUL)" refers to "the mounting method of directly burying the semiconductor chip in the recess of the printed wiring board and connecting the semiconductor chip to the wiring on the printed wiring board". [Example]

The present invention is specifically described below by means of examples, but the present invention is not limited to these examples. In addition, in the following description, unless otherwise indicated, "part" and "%" which show an amount mean "mass part" and "mass %", respectively.

(Synthesis Example 1: Synthesis of Resin (A-1)) 1,1'-bis(2,7-diglycidoxynaphthyl)methane with an epoxy equivalent of 162 ("EXA-4700", Dainippon Ink Chemical Industry Co., Ltd.) 162 parts were put into a flask equipped with a gas introduction tube, a stirring device, a cooling tube, and a thermometer, 340 parts of carbitol acetate were added, and heated to dissolve, 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 slowly added dropwise, and the reaction was carried out for 16 hours. This reaction product was cooled to 80-90 degreeC, 80 parts of tetrahydrophthalic anhydrides were added, it was made to react for 8 hours, and it cooled. Thus, a resin solution having an acid value of 90 mgKOH/g of solid content (non-volatile content of 70%, hereinafter abbreviated as "A-1") was obtained.

<Examples 1 to 5 and Comparative Examples 1 to 6> Each component was blended at the blending ratio shown in the following table, and a high-speed rotary mixer was used to prepare a resin varnish. Next, a PET film ("LUMIRROR T6AM" manufactured by Toray Industries, Ltd., with a thickness of 38 μm and a softening point of 130° C.), which was subjected to mold release treatment with an alkyd resin-based mold release agent (“AL-5” manufactured by LINTEK Corporation), was prepared as a support. "Release PET"). The prepared resin varnish was uniformly coated on the mold release PET in such a way that the thickness of the dried photosensitive resin composition layer was 40 μm using a die-nozzle coater, and dried from 80° C. to 110° C. for 6.5 minutes to obtain a A photosensitive film with a support with a photosensitive resin composition layer on a mold release PET.

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

<Evaluation of resolution, crack resistance, and undercut resistance> (Formation of laminate for evaluation) The copper layer of the glass epoxy substrate (copper-clad laminate) in which a copper layer with a thickness of 18 μm was patterned to form a circuit was obtained by The surface treatment agent (CZ8100, the product made by MERCK company) containing an organic acid was processed and roughened. Next, the photosensitive resin composition layers of the photosensitive films with supports obtained in Examples and Comparative Examples were arranged so as to be in contact with the surface of the copper circuit, and were laminated using a vacuum laminator (manufactured by NIKKO Materials Co., Ltd., VP160) to form A laminate in which the copper-clad laminate, the photosensitive resin composition layer, and the support are sequentially laminated. The crimping conditions were set as a vacuuming time of 30 seconds, a crimping temperature of 80° C., a crimping pressure of 0.7 MPa, and a pressing time of 30 seconds. The laminate was allowed to stand at room temperature for more than 30 minutes, and was exposed to ultraviolet rays using a circular hole punching machine and a patterning device from the support of the laminate. Exposure pattern uses opening: 50μm/60μm/70μm/80μm/90μm/100μm round hole, L/S (line/space): 50μm/50μm, 60μm/60μm, 70μm/70μm, 80μm/80μm, 90μm/90μm, 100μm/100μm lines and spaces, and a quartz glass mask depicting a 1cm×2cm square. After standing at room temperature for 30 minutes, the support was peeled off from the aforementioned laminate. On the entire surface of the photosensitive resin composition layer on the laminate, a 30° C. 1 mass % sodium carbonate aqueous solution as a developer was subjected to spray development for 2 minutes at a spray pressure of 0.2 MPa. After spray development, 1 J/cm ² of ultraviolet rays were irradiated, and further heat treatment was performed at 180° C. for 30 minutes to form an insulating layer having openings on the laminate. This was used as a laminate for evaluation.

(Evaluation of resolution) The unexposed part of the quadrangular portion of 1 cm × 2 cm of the laminate for evaluation was visually observed. When the resin was not left in the unexposed part, it was marked with ○, and when the resin was visually confirmed, it was marked with x. Next, the formed guide hole and L/S were observed by SEM (magnification of 1000 times), and the minimum guide hole diameter and minimum L/S without residue were measured. In addition, the L/S shape was evaluated according to the following criteria. ○: Observe the L/S of three points, and there is no peeling or embedding between all the L/S. ×: Observe the L/S of three points, and see the resin embedded or peeled between any L/S.

(Evaluation of crack resistance) The laminate for evaluation was exposed to the atmosphere at -65°C for 15 minutes, and then heated at a temperature increase rate of 180°C/min, and then exposed to the atmosphere at 175°C for 15 minutes. 180℃/min cooling speed cooling thermal cycle and processing test. After the test, the degree of cracking and peeling of the laminate for evaluation was observed with an optical microscope (manufactured by NIKON Corporation, "ECLIPSE LV100ND"), and the evaluation was performed according to the following criteria. ○: Cracks and peeling were not observed. ×: Cracks and peeling were observed.

(Evaluation of undercut resistance) Cross-section observation was carried out by SEM in the 100 μm guide hole formed in the laminate for evaluation, and the radius (a (μm)) and the bottom radius (b (μm)) of the uppermost part of the cross-section were measured, and the Difference.

<Measurement of Average Linear Thermal Expansion Coefficient and Glass Transition Temperature> (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 subjected to ultraviolet rays of 100 mJ/cm ² . The exposure is photohardened. Then, the whole surface of the photosensitive resin composition layer was spray-developed with a 1 mass % sodium carbonate aqueous solution at 30° C. as a developing solution at a spray pressure of 0.2 MPa for 2 minutes. After spray development, 1 J/cm ² of ultraviolet rays were irradiated, and further heat treatment was performed at 190° C. for 90 minutes to form a cured product. Then, the support was peeled off to obtain a hardened product for evaluation.

(Measurement of Average Linear Thermal Expansion Coefficient) The cured product for evaluation was cut into test pieces having a width of 5 mm and a length of 15 mm, and a thermomechanical analysis was performed by a tensile weighting method using a thermomechanical analyzer (Thermo Plus TMA8310, manufactured by Rigaku Corporation). After the test piece was attached to the above-mentioned apparatus, it was continuously measured twice under the measurement conditions of a load of 1 g and a temperature increase rate of 5°C/min. The average linear thermal expansion coefficient (ppm) from 25°C to 150°C in the second measurement was calculated.

(Measurement of glass transition temperature) The cured product for evaluation was cut into test pieces of about 5 mm in width and about 15 mm in length, and thermomechanical analysis was performed by the tensile weighting method using a dynamic viscoelasticity measuring apparatus (EXSTAR6000, manufactured by SII Technology). After the test piece was attached to the aforementioned apparatus, the measurement was performed under the measurement conditions of a load of 200 mN and a temperature increase rate of 2°C/min. The peak top of the obtained tan δ was calculated as the glass transition temperature (°C).

The resins used are as follows. (A) Component ・ZFR-1491H: Bisphenol F-type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH/g, solid content concentration about 70%) ・ZAR-2000: Bisphenol A-type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99mgKOH/g, solid content concentration about 70%) ・ZCR-1569H: Biphenyl type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 98mgKOH/g, solid content concentration about 70%) %) A-1: Resin (A-1) synthesized in Synthesis Example 1 Component (B)

‧SC4050: Surface-treated 100 parts by mass of fused silica (manufactured by ADMATECHS, average particle size 1.0 μm) with 0.5 part by mass of aminosilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573)

(C) Ingredient

‧Irgacure 379: 2-dimethylamino-2-(4-methyl-benzyl-1-(4-morpholin-4-yl-phenyl)-butan-1-one) (manufactured by BASF)

‧Irgacure 907: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one) (manufactured by BASF)

‧DETX-S: Photopolymerization initiator (2,4-diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.)

‧Irgacure TPO: 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide (manufactured by BASF)

‧Irgacure 819: bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide) (manufactured by BASF)

‧Irgacure OXE-01: 1,2-Octanedione-1-[4-(phenylthio)-2-(O-benzyl oxime)] (manufactured by BASF)

(D) Ingredient

‧NC3000H: Biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent about 272)

‧1031S: Tetrahydroxyphenylethane type epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent is about 200)

(E) Ingredient

‧DPHA: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., acrylic acid equivalent is about 96)

‧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 of the above table, it can be seen that the examples using the photosensitive resin composition of the present invention have good resolution, undercut resistance and crack resistance, a low average linear thermal expansion coefficient, and a high glass transition temperature.

On the other hand, in Comparative Examples 1 to 3, since the component (C) was not used, the undercut resistance was poor, and it was not usable as a photosensitive resin composition. In Comparative Examples 4 to 6, since the component (A) was not used, the resolution and crack resistance were poor, the average linear thermal expansion coefficient was high, and the glass transition temperature was low, and thus were not usable as photosensitive resin compositions. In addition, in Comparative Example 4, since the resolution was worse, the undercut resistance could not be evaluated.

It was confirmed that in each Example, even if the component (E) was not contained, the same result as in the above-mentioned Example was obtained, although the degree was inferior.

Claims (11)

A photosensitive resin composition comprising (A) a resin containing a naphthalene skeleton, an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler with an average particle size of 0.5 μm or more and 2.5 μm or less, (C) an acyl group Phosphine oxide-based photopolymerization initiator or oxime ester-based photopolymerization initiator, and (D) epoxy resin, the content of (B) component is when the total solid content of the photosensitive resin composition is 100% by mass is 60 mass % or more and 85 mass % or less, and the glass transition temperature of the cured product after photocuring the photosensitive resin composition and then thermally curing at 190° C. for 90 minutes is 170° C. or more. The photosensitive resin composition according to claim 1, wherein the component (C) is bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, 2,4,6-trimethylbenzyl Any of acyl-diphenyl-phosphine oxide and 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzyl oxime)]. The photosensitive resin composition according to claim 1, wherein the component (A) contains an epoxy (meth)acrylate containing an acid-modified naphthalene skeleton. The photosensitive resin composition according to claim 1, wherein the component (D) comprises at least one of a biphenyl-type epoxy resin and a tetraphenylethane-type epoxy resin. The photosensitive resin composition according to claim 1, wherein the component (B) contains silicon oxide. A photosensitive resin composition comprising (A) a resin containing a naphthalene skeleton, an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler with an average particle size of 0.5 μm or more and 2.5 μm or less, (C) an acyl group Phosphine oxide-based photopolymerization initiator or oxime ester-based photopolymerization initiator, and (D) epoxy resin, the content of (B) component is when the total solid content of the photosensitive resin composition is 100% by mass , is 60 mass % or more and 85 mass % or less, and (A) component is selected from the group consisting of (1) 1,3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyl ( 2) Polyhydroxy binaphthyl-type epoxy resins; (3) Naphthalene-type epoxy resins having a skeleton obtained by the condensation reaction of polyhydroxy naphthalene and aldehydes; and (4) At least 1 of the binaphthol-type epoxy resins It is an epoxy ester resin containing acid-modified unsaturated naphthalene skeleton obtained by reacting a naphthalene type epoxy compound with an unsaturated carboxylic acid, and then reacting with an acid anhydride. A photosensitive film, which contains the feeling as in any one of claims 1 to 6 Optical resin composition. A photosensitive film with a support, comprising a support and a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 6 provided on the support. 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 6. The printed wiring board of claim 9, wherein the insulating layer is a solder resist. A semiconductor device comprising the printed wiring board as claimed in claim 9.