TW202136911A - Photosensitive resin composition, two-fluid photosensitive resin composition, dry film, and printed wiring board having properties of high heat resistance, and prevention of reduced adhesion strength - Google Patents

Abstract

The present invention provides a photosensitive resin composition with high heat resistance, prevention property of reduced adhesion strength, and thermal cycling resistance. The photosensitive resin composition of the present invention is characterized in containing: at least one of a carboxyl group-containing resin, talc, and mica; a bifunctional or higher functional (meth) acrylate with an isocyanuric acid ring; an epoxy resin; and a photopolymerization initiator.

Description

Photosensitive resin composition, two-component photosensitive resin composition, dry film, and printed wiring board

The present invention relates to a photosensitive resin composition, a two-component photosensitive resin composition, a dry film, and a printed wiring board.

Generally speaking, for printed wiring boards used in electronic equipment, etc., when electronic parts are mounted on the printed wiring board, to prevent solder adhesion to unnecessary parts, form a barrier in the area where the connection hole on the substrate with the circuit pattern is removed. Welding layer. Nowadays, the solder resist layer is a cured product that is mainly cured by heating or irradiating the patterned resin with a photosensitive resin composition applied to the substrate, exposed and developed to form a pattern, and the so-called light Solder masks have become the mainstream, and such photosensitive resin compositions are generally required to have high solder heat resistance.

In recent years, the development of electric vehicles is rapidly progressing, and the above-mentioned substrates with solder resist layers are applied. Power semiconductors for large power control such as electric cars, hybrid cars, or wind power generation devices that want to control such as electric cars, hybrid cars, or wind power generation devices generate a lot of heat, and substrates suitable for this are exposed to high-temperature environments for a long time. Therefore, it is expected that the photosensitive resin composition not only has heat resistance, but does not decrease the adhesion force even in such a high-temperature environment, and has high adhesion strength prevention properties. In addition, the power semiconductor becomes extremely high temperature when it is energized, and becomes low temperature when it is not energized. Repeatedly, cracks are likely to occur in the solder resist layer. The photosensitive resin composition is required to have high resistance to cold and heat cycles.

Among them, in Patent Document 1, a photosensitive resin composition containing a photosensitive insulating resin, a thermosetting insulating resin, a polyfunctional acrylate having a triazine ring, and acrylonitrile butadiene is proposed, but the adhesion force is prevented from being reduced There is room for improvement in performance and resistance to cold and heat cycles.

In addition, in Patent Document 2, the purpose of improving heat resistance is to add triglycidyl triisocyanurate to the photosensitive resin composition. However, in recent years, due to the environmental impact of mutations, etc., the use has been gradually controlled. In addition, the cured product formed using the photosensitive resin composition has a problem of deterioration in resistance to cold and heat cycles. Therefore, photosensitive compositions having excellent heat resistance and resistance to cold and heat cycles are expected. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2003-66603 A [Patent Document 2] JP 9-185167 A

[Problem Solved by Invention]

Therefore, the object of the present invention is to provide a photosensitive resin composition having high heat resistance, prevention of adhesion reduction, and resistance to cold and heat cycles. In addition, another object of the present invention is to provide a dry film, a cured product, and a printed wiring board formed using the aforementioned photosensitive resin composition. [Means to solve the problem]

The photosensitive resin composition according to the present invention is characterized by containing: at least any one of a carboxyl group-containing resin, talc and mica, a (meth)acrylate having an isocyanuric ring-containing bifunctional or more functional (meth)acrylate, and an epoxy resin With photopolymerization initiator.

In the aspect of the present invention, as the carboxyl group-containing resin in the photosensitive resin composition, at least one of a novolak type carboxyl group-containing resin and a bisphenol type carboxyl group-containing resin is preferred.

In the aspect of the present invention, the photosensitive resin composition preferably contains at least any one of silicon oxide and alumina.

With regard to the aspect of the present invention, the photosensitive resin composition preferably contains a (meth)acrylate having a bifunctional or more functional group that does not have an isocyanuric acid ring.

In the aspect of the present invention, the photosensitive resin composition preferably contains fluorine-containing mica as mica.

The two-component curable photosensitive resin composition of the present invention is composed of a first composition and a second composition, and is characterized by: The first composition contains a carboxyl group-containing resin and a photopolymerization initiator; The second composition contains epoxy resin; At least any one of the first composition and the second composition contains at least any one of talc and mica; and At least any one of the first composition and the second composition contains a (meth)acrylate having a bifunctional or more functional isocyanurate ring.

In the aspect of the present invention, the first composition preferably contains at least any one of talc and mica.

Regarding the aspect of the present invention, it is preferable that the second composition contains a (meth)acrylate having an isocyanuric ring and more than bifunctional (meth)acrylate.

In the aspect of the present invention, the first composition preferably contains at least any one of silicon oxide and aluminum oxide.

Regarding the aspect of the present invention, it is preferable that the first composition contains a (meth)acrylate having a bifunctional or higher function that does not have an isocyanuric acid ring.

The dry film of the present invention is characterized by having: a film; and a resin layer obtained by coating the photosensitive resin composition or the two-component photosensitive resin composition on the film and drying.

The printed wiring board of the present invention is characterized in that it is obtained by curing the photosensitive resin composition, the two-component photosensitive resin composition, or the resin layer of the dry film. [Effects of Invention]

According to the present invention, it is possible to provide a photosensitive resin composition having high heat resistance, prevention of adhesion reduction, and resistance to cold and heat cycles. In addition, according to another aspect of the present invention, a dry film, a cured product, and a printed wiring board formed using the aforementioned photosensitive resin composition can be provided.

[Types of Implementation of Invention]

[Photosensitive resin composition in the first aspect] In the first aspect, the photosensitive resin composition contains at least any one of a carboxyl group-containing resin, talc, and mica, a (meth)acrylate having an isocyanuric ring-containing bifunctional or more functional (meth)acrylate, and an epoxy resin With photopolymerization initiator. In addition, the photosensitive resin composition may contain inorganic fillers other than talc and mica (hereinafter referred to as other inorganic fillers), bifunctional or higher (meth)acrylates without isocyanuric acid rings, colorants, and At least one organic solvent. The following is a detailed description of each component.

[(1) Resin containing carboxyl group] As the carboxyl group-containing resin, various resins known in the past having a carboxyl group in the molecule can be used. The photosensitive resin composition has a carboxyl group-containing resin and can impart alkali developability to the photosensitive resin composition. In particular, a carboxyl group-containing resin having an ethylenically unsaturated double bond in the molecule is preferable from the viewpoint of photocurability or development resistance. The ethylenically unsaturated double bond is preferably acrylic acid, methacrylic acid, or those derived from these derivatives. When only a carboxyl group-containing resin that does not have an ethylenically unsaturated double bond is used, it can be used in combination with (meth)acrylates such as (meth)acrylates such as (meth)acrylates having an isocyanuric ring, which are described later, The composition has photosensitivity. As a specific example of a carboxyl group-containing resin, the compound shown below (any one of oligomer and polymer may be sufficient) is mentioned.

(1) Copolymerization of unsaturated carboxylic acids such as (meth)acrylic acid with compounds containing unsaturated groups such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc. Resins containing carboxyl groups.

(2) Diisocyanates such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, etc., and dimethylol propionic acid, dimethylol butanoic acid and other carboxyl-containing diisocyanates Alcohol compound and polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A epoxy adduct diol, phenolic hydroxyl group Carboxyl group-containing urethane resin for the polyaddition reaction of glycol compounds such as compounds with alcoholic hydroxyl groups.

(3) With diisocyanate, combined with bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisxylenol epoxy resin , Bisphenol type epoxy resin and other bifunctional epoxy resin (meth)acrylate or its partial acid anhydride modification, carboxyl-containing diol compound and diol compound polyaddition reaction of carboxyl-containing photosensitive amine Alkyl formate resin.

(4) In the synthesis of the resin of (2) or (3), it is added to a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as a hydroxyalkyl (meth)acrylate, And the carboxyl group-containing photosensitive urethane resin which undergoes terminal (meth)acrylation.

(5) In the synthesis of the resin of (2) or (3), an isomolar reactant of isophorone diisocyanate and pentaerythritol triacrylate is added, which has one isocyanate group and more than one in the molecule A (meth)acrylic compound is a carboxyl group-containing photosensitive urethane resin whose terminal is (meth)acrylated.

(6) A carboxyl group-containing photosensitive resin in which (meth)acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin, and a dibasic acid anhydride is added to the hydroxyl group present in the side chain.

(7) The polyfunctional epoxy resin in which the hydroxyl group of the bifunctional (solid) epoxy resin is further epoxidized by epichlorohydrin is reacted with (meth)acrylic acid, and the generated hydroxyl group is subjected to dibasic acid anhydride. Addition of carboxyl-containing photosensitive resin.

(8) The bifunctional oxetane resin is reacted with dicarboxylic acids such as adipic acid, phthalic acid and hexahydrophthalic acid, and phthalic anhydride, four Hydrophthalic anhydride, hexahydrophthalic anhydride and other dibasic acid anhydrides are added with carboxyl group-containing polyester resin.

(9) For epoxy compounds having multiple epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (former Base) acrylic acid and other unsaturated group-containing monocarboxylic acids are reacted, and the alcoholic hydroxyl group of the obtained reaction product is made of maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc. A carboxyl group-containing photosensitive resin obtained by reacting an acid anhydride.

(10) The reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an epoxide such as ethylene oxide and propylene oxide is reacted with an unsaturated group-containing monocarboxylic acid to obtain The reaction product is a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride.

(11) For the reaction organism obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate and propylene carbonate, the unsaturated group-containing monomer A carboxyl group-containing photosensitive resin obtained by reacting a carboxylic acid and reacting a polybasic acid anhydride on the obtained reaction product.

(12) For the resins of (1) to (11) above, a carboxyl group-containing compound obtained by addition of a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule Photosensitive resin. In addition, in this specification, the term “(meth)acrylate” is a term that uses acrylate, methacrylate, and these mixtures as a generic term, and the same applies to other similar expressions.

The acid value of the carboxyl-containing resin is preferably 40-150 mgKOH/g. By setting the acid value of the carboxyl group-containing resin to 40 mgKOH/g or more, the alkaline development can be improved. In addition, by setting the acid value below 150 mgKOH/g, it is easy to draw a good resist pattern. Preferably it is 50-130 mgKOH/g.

Although the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, it is generally preferably 2,000-150,000. By setting the weight average molecular weight above 2,000, the non-stick performance or resolution can be improved. In addition, when the weight average molecular weight is set to 150,000 or less, the developability or storage stability can be improved. Preferably it is 5,000 to 100,000.

The blending amount of the carboxyl group-containing resin in the photosensitive resin composition is preferably 20 to 60% by mass in terms of solid content. If it is set to 20% by mass or more, the strength of the coating film can be further improved. In addition, if it is set to 60% by mass or less, the viscosity can be appropriately changed and the printability can be improved. Preferably it is 30-50 mass %.

[(2) Talc and Mica] The photosensitive resin composition contains at least any one of talc and mica, and by this, it is possible to improve the adhesion reduction prevention property of the photosensitive resin composition and the resistance to cold and heat cycles.

The average particle size (D50) of talc is preferably 0.1 μm to 100 μm, preferably 1 μm to 50 μm. By setting the above-mentioned particle diameter within the range, the dispersibility of talc in the photosensitive resin composition can be further improved. Here, the so-called D50 means the particle size in 50% of the cumulative volume obtained by the laser diffraction scattering particle size distribution method based on the Mie scattering theory. More specifically, a laser diffraction scattering type particle size distribution measuring device is used to prepare the particle size distribution of fine particles on a volume basis, and the median diameter can be measured as the average particle size. As the measurement sample, it is preferable to use one that disperses fine particles in water by ultrasonic waves. As a laser diffraction particle size distribution measuring device, LA-500 manufactured by Horiba Co., Ltd., etc. can be used.

When the blending amount of talc in the photosensitive resin composition is converted into solid content, it is preferably 1 to 200 parts by mass, and more preferably 10 to 150 parts by mass for 100 parts by mass of the carboxyl group-containing resin. Thereby, it is possible to further improve the adhesion drop prevention property of the photosensitive resin composition and the resistance to cold and heat cycles.

The mica used in the present invention may be swelling, non-swelling, synthetic, or non-synthetic. Among the various kinds of mica, fluorine-containing mica is used as good. The use of fluorine-containing mica can further improve the heat resistance and thermal cycle resistance of the photosensitive resin composition.

The average particle size (D50) of the mica is preferably 0.1 μm to 500 μm, preferably 1 μm to 300 μm. By setting the above-mentioned particle diameter within this range, the dispersibility of mica in the photosensitive resin composition can be further improved.

The compounding amount of mica in the photosensitive resin composition, in terms of solid content, is preferably 1 to 200 parts by mass, preferably 10 to 150 parts by mass for 100 parts by mass of the carboxyl group-containing resin . Thereby, the heat resistance of the photosensitive resin composition, the prevention of adhesion reduction, and the resistance to cold and heat cycles can be further improved.

[(3) (Meth)acrylates having two or more functions with isocyanuric acid ring] The photosensitive resin composition contains a (meth)acrylate having a bifunctional or more functional isocyanurate ring, thereby improving the heat resistance of the photosensitive resin composition, the prevention of adhesion reduction, and the resistance to cold and heat cycles.

Examples of usable (meth)acrylates having an isocyanuric ring-containing bifunctional or more functional (meth)acrylate include, for example, ethoxylated isocyanuric acid di(meth)acrylate and ethoxylated isocyanurea Acid tri(meth)acrylate, propoxylated isocyanurate di(meth)acrylate, propoxylated isocyanurate tri(meth)acrylate, and caprolactone modified products of these.

The compounding amount of the (meth)acrylate having an isocyanuric ring-containing bifunctional or more functional (meth)acrylate in the photosensitive resin composition, in terms of solid content, is 1 to 100 parts by mass of the carboxyl group-containing resin It is preferably 50 parts by mass, and more preferably 5-40 parts by mass. Thereby, the heat resistance of the photosensitive resin composition, the prevention of adhesion reduction, and the resistance to cold and heat cycles can be further improved.

[(4) Epoxy] Examples of usable epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, and bisphenol S Type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentane Diene type epoxy resin, triphenylmethane type epoxy resin, etc. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of epoxy resins sold include jER828, 806, 807, YX-8000, 8034, jER834 manufactured by Mitsubishi Chemical Corporation, YD-128, YDF-170 manufactured by Nippon Steel & Sumitomo Metal Co., Ltd. ZX-1059, ST-3000, 830, 835, 840, 850, N-730A, N695 manufactured by DIC Co., Ltd., and RE-306 manufactured by Nippon Kayaku Co., Ltd.

The epoxy equivalent of the epoxy resin in the photosensitive resin composition is, in terms of solid content, the equivalent 1 of the carboxyl group of the carboxyl group-containing resin is preferably 0.3 to 3.0. If the amount is 0.3 equivalent or more, the residue of the carboxyl group in the cured film can be prevented, and good heat resistance, alkali resistance, electrical insulation, etc. can be obtained. On the other hand, when the above-mentioned compounding amount is set to 3.0 equivalents or less, it is possible to prevent the low molecular weight cyclic (thio) ether from remaining on the dry coating film, and to ensure the strength of the cured coating film.

[(5) Photopolymerization initiator] As the photopolymerization initiator that can be used, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl- 2-Dimethylamino-1-(4-morpholinophenyl)-butane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl ]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone and other α-aminoacetophenone photopolymerization initiators: 1-hydroxy-cyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1 -{4-[4-(2-Hydroxy-2-methyl-propanyl)-benzyl]phenyl}-2-methyl-propane-1-one, 2-hydroxy-2-methyl- Hydroxyacetophenone-based photopolymerization initiators such as 1-phenylpropane-1-one; bis-(2,6-dichlorobenzyl)phenyl phosphine oxide, bis-(2,6-dichlorobenzene) Methyl)-2,5-dimethylphenyl phosphine oxide, bis-(2,6-dichlorobenzyl)-4-propylphenyl phosphine oxide, bis-(2,6-dichloro) Benzyl)-1-naphthalene phosphine oxide, bis-(2,6-dimethoxybenzyl)phenyl phosphine oxide, bis-(2,6-dimethoxybenzyl)- 2,4,4-Trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4, 6-trimethylbenzyl)-phenyl phosphine oxide, 2,6-dimethoxybenzyl diphenyl phosphine oxide, 2,6-dichlorobenzyl diphenyl phosphine oxide, 2,4,6-Trimethylbenzylphenylphosphonic acid methyl ester, 2-methylbenzyldiphenylphosphine oxide, neopentylphenylphosphonic acid isopropyl ester, 2, Phosphine oxide-based photopolymerization initiators such as 4,6-trimethylbenzyl diphenyl phosphine oxide; benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether , Benzoin isopropyl ether, benzoin n-butyl ether and other benzoin-based photopolymerization initiators; benzoin alkyl ether-based photopolymerization initiators; benzophenone, p-methylbenzophenone, Michler’s ketone , Methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone and other benzophenone-based photopolymerization initiators; acetophenone , 2,2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl Acetophenone-based photopolymerization initiators such as phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-acetone; thioxanthone, 2- Ethylthioxanthone, 2-isopropylthioxanthone, 2,4-Dimethylthioxanthone, 2,4-Diethylthioxanthone, 2-chlorothioxanthone Thioxanthone-based photopolymerization initiators such as ketone, 2,4-diisopropylthioxanthone, etc.; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert -Anthraquinone-based photopolymerization initiators such as butylanthraquinone, 1-chloroanthraquinone, 2-pentylanthraquinone, 2-aminoanthraquinone; acetophenone dimethyl Ketal photopolymerization initiator such as methyl ketal and benzyl dimethyl ketal; ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzyl Benzoic acid ester-based photopolymerization initiators such as benzoic acid ester, p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O -Benzyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyl) Oxime) and other oxime ester-based photopolymerization initiators; bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl) Phenyl) titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyrrol-1-yl)ethyl)phenyl]titanium and other titanocene photopolymerization Starter and so on. A photopolymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of commercially available α-aminoacetophenone-based photopolymerization initiators include Omnirad 907, Omnirad 369, and Omnirad 379 manufactured by IGM Resins. Examples of commercially available phosphine oxide-based photopolymerization initiators include Omnirad TPO manufactured by IGM Resins, Omnirad 819, and the like.

Moreover, it can also be applied to the photopolymerization initiator which has two oxime ester groups in a molecule|numerator, Specifically, the oxime ester compound which has a carbazole structure shown by the following general formula is mentioned.

In the above formula, X represents a hydrogen atom, an alkyl group having 1 to 17 carbons, an alkoxy group having 1 to 8 carbons, a phenyl group, and a phenyl group. Alkoxy group, amino group, alkylamino group or dialkylamino group of alkyl group with 1 to 8 carbon atoms), naphthyl group (from alkyl group with 1 to 17 carbon atoms, 1 to 8 carbon atoms) Alkoxy group, amino group, alkylamino group or dialkylamino group of a C 1-8 alkyl group), Y and Z each represent a hydrogen atom, a C 1-17 alkyl group, and a carbon number 1-8 alkoxy, halogen, phenyl, phenyl (comprised of alkyl groups having 1 to 17 carbons, alkoxy groups having 1 to 8 carbons, amino groups, and alkyl groups having 1 to 8 carbons Alkylamino group or dialkylamino group substituted), naphthyl group (comprised of alkyl groups having 1 to 17 carbons, alkoxy groups having 1 to 8 carbons, amino groups, and alkyl groups having 1 to 8 carbons) Alkylamino group or dialkylamino group substituted), anthracenyl, pyridyl, benzofuranyl, benzothienyl, Ar represents alkylene, vinylene, phenylene having 1 to 10 carbon atoms, Biphenyl, pyridinyl, naphthyl, thiophene, anthracenyl, thiophene, furanyl, 2,5-pyrrol-diyl, 4,4'-stilbene-diyl, 4,2'-benzene Ethylene-diyl, n is an integer of 0 or 1.

Especially in the above formula, X and Y are each methyl or ethyl, Z is methyl or phenyl, n is 0, and Ar is phenylene, naphthylene, thiophene or thiophene.

In addition to the aforementioned photopolymerization initiators, benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds can also be used as photopolymerization initiators. Agent and use. However, rather than using these alone as a photopolymerization initiator, the above-mentioned photopolymerization initiator can be used in combination, and it is better for the user as a photopolymerization initiator or sensitizer. Among the above, also from the viewpoint of deep curing properties, thioxanthone compounds and tertiary amine compounds are preferred, and thioxanthone compounds are preferred. In addition, two or more of the above-mentioned compounds may be used in combination.

The blending amount of the photopolymerization initiator in the photosensitive resin composition is preferably 1-50 parts by mass, and 1-20 parts by mass for 100 parts by mass of the carboxyl group-containing resin in terms of solid content. The one is better. Thereby, the hardenability of the deep part can be improved. In addition, when the photosensitive resin composition contains the above-mentioned benzoin compound as a photopolymerization initiation assistant, etc., the compounding amount is 0.01-10 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin when calculated as solid content Preferably, it is preferably 0.1 to 5 parts by mass. With this, the hardening of the deep part can be improved.

[(6) Other inorganic fillers] The photosensitive resin composition of the present invention preferably contains inorganic fillers other than talc and mica. Thereby, it is possible to further improve the adhesion reduction resistance of the photosensitive resin composition and the resistance to cold and heat cycles.

Other inorganic fillers include amorphous silica, crystalline silica, fused silica, spherical silica and other silicon oxides, alumina, calcium oxide, magnesium oxide, zinc oxide, and calcium carbonate. , Magnesium carbonate, fly ash, dehydrated sludge, natural silica, synthetic silica, kaolin, clay, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, hydrotalcite, aluminum silicate, magnesium silicate, silicon Calcium acid, Wollastonite, potassium titanate, magnesium sulfate, calcium sulfate, magnesium phosphate, sepiolite, xonotlite, boron nitride, aluminum borate, silica balls, glass flakes, glass balls, Silica, iron slag, copper, iron, iron oxide, sendust, alnico magnet, various ferrite and other magnetic powder, cement, glass powder, Neuburg silica, diatomaceous earth, trioxide Antimony, magnesium oxysulfuric acid, water and aluminum, water and gypsum, alum and barium sulfate, etc. Other inorganic fillers can be used alone or in combination of two or more. Among the above, it is also preferable to contain at least one of silicon oxide and aluminum oxide, and it can be used in combination with two types of spherical silicon dioxide and aluminum oxide, because the heat resistance and heat resistance of the photosensitive resin composition can be significantly improved. It has better resistance to hot and cold cycles.

The average particle diameter (D50) of other inorganic fillers is preferably 0.1-100 μm, and more preferably 0.1-50 μm.

The blending amount of other inorganic fillers in the photosensitive resin composition, in terms of solid content, is preferably 1 to 500 parts by mass, and preferably 10 to 300 parts by mass for 100 parts by mass of the carboxyl group-containing resin For better. Thereby, it is possible to further improve the adhesion reduction resistance of the photosensitive resin composition and the resistance to cold and heat cycles. In addition, from the viewpoints of the prevention of adhesion reduction of the photosensitive resin composition and the resistance to cold and heat cycles, the blending amount of barium sulfate in the photosensitive resin composition is based on the solid content of 100 masses of resin containing carboxyl groups. In terms of parts, it is preferably 50 parts by mass or less, preferably 10 parts by mass or less, and particularly preferably not contained.

When spherical silica and alumina are contained in the photosensitive resin composition, the content ratio to talc and mica (the sum of talc and mica content: spherical silica: alumina) is based on the mass standard. 1: 0.1 to 99: 0.1 to 99 is preferred, and 1: 0.1 to 9: 0.1 to 9 is preferred. Thereby, the heat resistance and the resistance to cold and heat cycles of the photosensitive resin composition can be further improved.

[(7) Bifunctional or higher (meth)acrylate without isocyanuric acid ring] It is preferable that the photosensitive resin composition of this invention contains the (meth)acrylate more than bifunctional which does not have an isocyanuric acid ring. This can further improve the heat resistance and the resistance to cold and heat cycles of the photosensitive resin composition.

Examples of usable (meth)acrylates having no isocyanuric acid ring and more than bifunctional (meth)acrylates include trimethylolpropane tri(meth)acrylate and ethoxylated trimethylolpropane Tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, ethoxylated propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate Base) acrylate, ethoxylated pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, ethoxylated propoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra (Meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol tetra (meth) acrylate, ethoxylated propoxylated pentaerythritol tetra (meth) acrylate, Ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and these caprolactone modified products. The bifunctional or more (meth)acrylate which does not have an isocyanuric acid ring may be used individually by 1 type, and may be used in combination of 2 or more types.

In the photosensitive resin composition, the compounding amount of the bifunctional or higher (meth)acrylate that does not have an isocyanuric ring is 1 to 100 parts by mass of the carboxyl group-containing resin when calculated in terms of solid content. It is preferably 50 parts by mass, and more preferably 10-50 parts by mass. This can further improve the heat resistance and the resistance to cold and heat cycles of the photosensitive resin composition.

[(8) Colorant] A coloring agent may be contained in the photosensitive resin composition. As the coloring agent, known coloring agents such as red, blue, green, and yellow can be used, and it can be any of pigments, dyes, and pigments. However, from the viewpoint of environmental load reduction and the impact on the human body, it is better to not contain halogen.

As red colorants, there are monoazo, bisazo, azo dye, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone Departments, etc., specifically include those with a color index (CI; issued by The Society of Dyersand Colourists) number as shown below.

Examples of monoazo red colorants include Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269, etc. In addition, as disazo-based red colorants, Pigment Red 37, 38, 41 and the like can be cited. Also, as monoazo dye-based red colorants, Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:1, 50:1, 52:1, 52 : 2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, 68, etc. In addition, as the benzimidazolone-based red colorant, Pigment Red 171, 175, 176, 185, 208 and the like can be mentioned. In addition, as perylene-based red colorants, Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224 and the like can be mentioned. In addition, as diketopyrrolopyrrole-based red colorants, Pigment Red 254, 255, 264, 270, 272 and the like can be mentioned. In addition, as a condensed azo-based red colorant, Pigment Red 220, 144, 166, 214, 220, 221, 242 and the like can be mentioned. Furthermore, as an anthraquinone-based red coloring agent, Pigment Red 168, 177, 216, Solvent Red 149, 150, 52, 207 and the like can be mentioned. In addition, as quinacridone-based red colorants, Pigment Red 122, 202, 206, 207, 209 and the like can be mentioned.

As the blue coloring agent, there are phthalocyanine series and anthraquinone series, and the pigment series can be exemplified by compounds classified as pigments, such as Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15: 6, 16, 60. As the dye system, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70, etc. can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds may also be used.

Examples of yellow colorants include monoazo, bisazo, condensed azo, benzimidazolone, isoindoline, anthraquinone, etc., for example, as an anthraquinone yellow colorant, Examples include Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, and 202. Examples of the isoindoline-based yellow coloring agent include Pigment Yellow 110, 109, 139, 179, 185 and the like. As a condensed azo-based yellow colorant, Pigment Yellow 93, 94, 95, 128, 155, 166, 180, etc. As the benzimidazolone-based yellow coloring agent, Pigment Yellow 120, 151, 154, 156, 175, 181 and the like can be mentioned. Also, as monoazo yellow colorants, Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183, etc. Also, as disazo yellow colorants, Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, etc.

Other colorants such as purple, orange, brown, black and white can also be added. Specifically, Pigment Black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32, Pigment Violet 19, 23, 29 , 32, 36, 38, 42, Solvent Violet 13, 36, CIPigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63 , 64, 71, 73, PigmentBrown 23, 25, carbon black, titanium oxide, etc.

The content of the coloring agent in the photosensitive resin composition is not particularly limited, but in terms of solid content, it is preferably set to 0.1 to 3 parts by mass for 100 parts by mass of the carboxyl group-containing resin. However, when the content of a white coloring agent such as titanium oxide is calculated in terms of solid content, it is preferably 0.1 to 200 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin.

[(9) Organic solvents] The photosensitive resin composition of the present invention may contain an organic solvent, whereby the viscosity can be adjusted. The usable organic solvent is not particularly limited, and examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, etc. . More specifically, ketones such as methyl ethyl ketone (MEK) and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, Carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; Ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate (carbitol acetate), dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether ethyl Esters such as acid esters, propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, naphtha, hydrogenated naphtha, Petroleum solvents such as solvent naphtha, etc. Such an organic solvent can be used individually by 1 type, and 2 or more types of mixtures can also be used.

The volatilization and drying of organic solvents can be achieved by using hot-air circulation drying ovens, IR ovens, hot plates, convection ovens, etc. (using a heat source equipped with an air heating method by steam, the hot air in the dryer is in countercurrent contact with the method and borrowing The method of spraying the support from the nozzle) is performed.

The content of the organic solvent in the photosensitive resin composition can be appropriately changed according to the materials constituting the photosensitive resin composition. For example, in terms of solid content, it is set to 10 for 100 parts by mass of the carboxyl group-containing resin. ~1000 parts by mass is preferred.

[Photosensitive resin composition in the second aspect] In the second aspect, the photosensitive resin composition is a two-component photosensitive resin composition composed of a first composition and a second composition. The "two-component photosensitive resin composition" in the present invention means a combination of a first composition and a second composition, that is, a mixture of these compositions. In this way, the photosensitive resin composition has a two-component type, so that the photosensitive resin composition can be made more resistant to a decrease in adhesion and resistance to cold and heat cycles. In addition, when the two-component photosensitive resin composition is used, it is better to mix the first composition and the second composition and stir them until they are uniform before use.

[First composition] The first composition contains at least a carboxyl group-containing resin and a photopolymerization initiator. In addition, the first composition preferably contains at least any one of talc and mica. Since the first composition contains at least any one of talc and mica, it is possible to further improve the cold and heat cycle resistance of the photosensitive resin composition. In addition, the first composition may contain a (meth)acrylate having an isocyanuric ring-containing bifunctional or more functional (meth)acrylate. In addition, the first composition preferably contains other inorganic fillers. Since the first composition contains other inorganic fillers, the cold and heat cycle resistance of the photosensitive resin composition can be further improved. In addition, the first composition preferably contains a bifunctional or higher (meth)acrylate that does not have an isocyanuric ring. The first composition contains bifunctional or higher (meth)acrylate without an isocyanurate ring, so that the heat resistance of the photosensitive resin composition can be further improved. In addition, the first composition may contain at least one of a colorant and an organic solvent. Specific examples of these constituent materials are as described above, and when the content is such that when the first composition and the second composition are mixed, the content is preferably the above content.

[Second composition] The second composition contains at least epoxy resin. In addition, the second composition may contain at least any one of talc and mica. In addition, the second composition is preferably one that contains a (meth)acrylate having an isocyanuric ring-containing bifunctional or more functional (meth)acrylate. Since the second composition contains a bifunctional or more functional (meth)acrylate having an isocyanuric acid ring, the thermal cycle resistance of the photosensitive resin composition can be further improved. In addition, the second composition may contain other inorganic fillers. In addition, the second composition may contain a bifunctional or higher (meth)acrylate that does not have an isocyanuric ring. In addition, the second composition may contain at least one of a colorant and an organic solvent. Specific examples of these constituent materials are as described above, and the content is preferably the above content when the first composition and the second composition are mixed.

As an inorganic filler in the first composition, the reason why (meth)acrylate having an isocyanuric ring is preferably contained in the second composition is not clarified, but it can be presumed to be as follows Show. That is, it is considered that the compatibility between the epoxy resin and the (meth)acrylate having an isocyanuric ring is good, and the (meth)acrylate having an isocyanuric ring can be sufficiently dispersed. . On the other hand, considering that the inorganic filler is contained in a composition having a carboxyl group-containing resin, the compatibility with organic components is compared with that of (meth)acrylates containing isocyanuric acid rings. The carboxyl resin is better, because it can be fully dispersed during curing. However, this is only the scope of speculation and is not necessarily limited to this.

[use] The photosensitive resin composition of the present invention is particularly suitable for printed wiring boards when forming a cured film. It can be used as a solder resist layer formation, interlayer insulating material, marking ink, cover film, soldering dam, and printed wiring board. The through hole of the perforation or the through hole or the hole of the recess is used as a filling material for burying the hole. Among these, it is also preferable to use it for the formation of a solder resist layer.

[Dry film] The dry film of the present invention is provided with a film, and a resin layer formed by the above-mentioned photosensitive resin composition or the above-mentioned two-component photosensitive resin composition that has been mixed and stirred. In addition, the dry film may have a protective film on the resin layer.

The materials of the film and the protective film are not particularly limited, but for example, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, and polyimide can be used. , Copper foil, aluminum foil, etc. On the surface of these films, it is better to apply surface treatment such as corona treatment. This can improve the adhesion to the resin layer.

The thickness of the film and the protective film is not particularly limited, but may be, for example, 5 μm to 50 μm.

The dry film can be produced by coating the photosensitive resin composition or the mixed and stirred two-component photosensitive resin composition on the film by a conventionally known method such as screen printing and drying. . In addition, the drying method is not particularly limited, and it can be performed by using a hot air circulation type drying furnace or the like.

[Printed Wiring Board] The printed wiring board of the present invention has a cured product formed from the above-mentioned photosensitive resin composition, the above-mentioned two-component photosensitive resin composition mixed and stirred, or the above-mentioned dry film resin layer.

As the printed wiring board of the present invention, for example, the curable resin composition of the present invention can be adjusted to a viscosity suitable for the coating method using the above-mentioned organic solvent, and then applied to the substrate by dip coating, flow coating, and roll coating. After coating by methods such as bar coating method, screen printing method, curtain coating method, etc., the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of 60 to 100°C to form a non-sticky Sexual resin layer. In the case of a dry film, the resin layer is bonded to the substrate while contacting the substrate with a laminate or the like, and then the carrier film is peeled to form a resin layer on the substrate.

As the above-mentioned base material, in addition to printed wiring boards or flexible printed wiring boards in which circuits are formed in advance by copper or the like, other examples include the use of paper phenol, epoxy paper, epoxy glass cloth, and glass polyamide. For high-frequency circuits such as imine, glass cloth/epoxy non-woven fabric, glass cloth/epoxy paper, epoxy synthetic fiber, fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate ester, etc. Copper-clad laminates and other materials of all grades (FR-4, etc.) copper-clad laminates. Other examples include metal substrates, polyimide films, polyethylene terephthalate films, and polyethylene naphthalate Ester (PEN) film, glass substrate, ceramic substrate, wafer board, etc.

The volatilization drying performed after coating the curable resin composition of the present invention can be carried out with a hot air circulation type drying furnace, IR furnace, hot plate, convection oven, etc. (using a heat source equipped with an air heating method by steam , The method of countercurrent contacting the hot air in the dryer and the method of spraying the support through the nozzle).

After the resin layer is formed on the substrate, a mask of a predetermined pattern is formed, and exposure is performed by selective active energy rays. ) Perform development to form a pattern of the hardened product. Furthermore, the cured product is irradiated with active energy rays and then heat-cured (for example, 100-220°C), or after heat-curing, irradiated with active energy rays, or only heat-cured to complete the final curing (main curing). It forms a cured film with excellent adhesion and hardness.

As the exposure machine used for the above-mentioned active energy ray irradiation, it is sufficient if it is equipped with a high-pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, mercury short arc lamp, etc., and can irradiate ultraviolet rays in the range of 350 to 450 nm. Also, a direct drawing device (for example, a laser direct imaging device that draws an image by a direct laser method using CAD data from a computer) can also be used. As the light source or laser light source of the direct scanner, the maximum wavelength can be in the range of 350-450nm. Although the amount of exposure to be imaged varies depending on the film thickness, etc., it is generally 10 to 1000 mJ/cm ² , and preferably can be set in the range of ^{20 to 800 mJ/cm 2.}

As the above developing method, dipping method, spray method, spray method, combing method, etc. can be used. As the developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate can be used. , Ammonia, amines and other alkaline aqueous solutions. [Example]

Next, examples are given to describe the present invention in more detail, but the present invention is not limited to these examples.

<Synthesis example: Preparation of carboxyl-containing resin paint A> The cresol novolac type epoxy resin (EOCN-104S manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 220g/eq) 220 parts by mass (1 equivalent), 140.1 parts by mass of carbitol acetate, and solvent stone 60.3 parts by mass of brain oil was added to the flask and dissolved by heating and stirring at 90°C. Once the obtained solution was cooled to 60°C, 72 parts by mass (1 mol) of acrylic acid, 0.5 parts by mass of methylhydroquinone, and 2 parts by mass of triphenylphosphine were added, and heated at 100°C for approximately 12 hours. After the reaction, a reactant with an acid value of 0.2 mgKOH/g was obtained. Here, 80.6 parts by mass (0.53 mol) of tetrahydrophthalic anhydride was added, and the reaction was carried out by heating at 90°C for about 6 hours to obtain a resin with a solid content of 85 mgKOH/g and a solid content concentration of 65.8%. Solution. Hereinafter referred to as carboxyl group-containing resin paint A.

<Synthesis example: Preparation of carboxyl-containing resin paint B> _{380 parts by mass of bisphenol F epoxy resin with X in the following general formula (1) as CH 2} and average degree of polymerization n of 6.2, and epoxy After 925 parts by mass of chloropropane was dissolved in 462.5 parts of dimethyl sulfide, 60.9 parts by mass (1.5 mol) of 98.5% NaOH was added at 70° C. with stirring for 100 minutes. After the addition, the reaction was carried out at 70°C for 3 hours.

After the completion of the reaction, 250 parts by mass of water was added and washed with water. After the oil and water are separated, from the oil layer, most of the dimethyl sulfide and excess unreacted epichlorohydrin are distilled and recovered under reduced pressure, and the reaction product containing the residual by-product salt and dimethyl sulfide is recovered , Dissolved in 750 parts by mass of methyl isobutyl ketone, and 10 parts by mass of 30% NaOH was added, and the reaction was carried out at 70° C. for 1 hour. After the completion of the reaction, water washing was performed twice with 200 parts by mass of water. After the oil and water are separated, the methyl isobutyl ketone is distilled and recovered from the oil layer to obtain an epoxy resin (a) with an epoxy equivalent of 310 g/eq and a softening point of 69°C. When the obtained epoxy resin (a) is calculated based on the epoxy equivalent, about 5 of the 6.2 alcoholic hydroxyl groups in the aforementioned starting material bisphenol F epoxy resin are epoxidized. 310 parts by mass of the epoxy resin (a) and 282 parts by mass of carbitol acetate were charged in a flask, and heated and stirred at 90° C. to be dissolved. Once the obtained solution was cooled to 60°C, 72 parts by mass (1 mol) of acrylic acid, 0.5 parts by mass of methylhydroquinone, and 2 parts by mass of triphenylphosphine were added, heated at 100°C, and reacted for about 60 hours to obtain A reactant with an acid value of 0.2mgKOH/g. 140 parts by mass (0.92 mol) of tetrahydrophthalic anhydride was added here, and it was heated at 90° C. to react until the acid value of the solid content reached 100 mgKOH/g to obtain a resin solution with a solid content concentration of 65%. Hereinafter referred to as carboxyl group-containing resin paint B.

<Synthesis example: Preparation of carboxyl-containing resin paint C> 380 parts by mass of bisphenol A epoxy resin with _{X in the above general formula (1) as C(CH 3} ) _{2 and average polymerization degree n of 6.2,} After dissolving 925 parts by mass of epichlorohydrin in 462.5 parts by mass of dimethyl sulfide, 60.9 parts by mass (1.5 mol) of 98.5% NaOH was added at 70° C. with stirring for 100 minutes. After the addition, the reaction was carried out at 70°C for 3 hours. After the completion of the reaction, 250 parts by mass of water was added and washed with water. After the oil and water are separated, from the oil layer, most of the dimethyl sulfide and excess unreacted epichlorohydrin are distilled and recovered under reduced pressure, and the reaction product containing the residual by-product salt and dimethyl sulfide is dissolved To 750 parts by mass of methyl isobutyl ketone, 10 parts by mass of 30% NaOH was further added, and the reaction was carried out at 70° C. for 1 hour. After the completion of the reaction, water washing was performed twice with 200 parts by mass of water. After the oil and water were separated, the methyl isobutyl ketone was distilled and recovered from the oil layer to obtain an epoxy resin (a) with an epoxy equivalent of 310 g/eq and a softening point of 69°C. When the obtained epoxy resin (a) is calculated from the epoxy equivalent, it is about 5 of the 6.2 alcoholic hydroxyl groups in the aforementioned starting material bisphenol F epoxy resin that are epoxidized. 310 parts by mass of the epoxy resin (a) and 282 parts by mass of carbitol acetate were put in a flask, and the mixture was heated and stirred at 90°C to be dissolved. Once the obtained solution was cooled to 60°C, 72 parts by mass (1 mol) of acrylic acid, 0.5 parts by mass of methylhydroquinone, and 2 parts by mass of triphenylphosphine were added, heated at 100°C, and reacted for about 60 hours to obtain A reactant with an acid value of 0.2mgKOH/g. 140 parts by mass (0.92 mol) of tetrahydrophthalic anhydride was added here, heated at 90°C, and reacted until the acid value of the solid content becomes 100 mgKOH/g to obtain a resin solution with a solid content concentration of 65%. Hereinafter referred to as carboxyl-containing resin paint C.

<Synthesis example: Preparation of carboxyl-containing resin paint D> In a four-necked flask equipped with a reflux cooler, a thermometer, a glass tube for nitrogen substitution, and a stirrer, 42 parts by mass of methacrylate, 43 parts by mass of methacrylate, 35 parts by mass of styrene, and benzyl were added. 35 parts by mass of acrylate, 100 parts by mass of carbitol acetate, 0.5 parts by mass of lauryl mercaptan, and 4 parts by mass of azobisisobutyronitrile were heated at 75°C for 5 hours under a nitrogen stream to perform polymerization reaction to obtain Copolymer solution (50 parts by mass of solid content). Here, 0.05 parts by mass of hydroquinone, 23 parts by mass of glycidyl methacrylate, and 2.0 parts by mass of dimethylbenzylamine were added, and the addition reaction was carried out at 80°C for 24 hours, and then carbitol acetic acid was added. 35 parts by mass of ester was obtained to obtain a copolymerized resin solution having an aromatic ring with a solid content concentration of 50% by mass. Hereinafter referred to as carboxyl group-containing resin paint D.

Example 1-1 <Preparation of photosensitive resin composition> The carboxyl group-containing resin paint A obtained as described above, LMP-100 talc manufactured by Fuji Talc Co., Ltd., as an ethoxylated isocyanurate ring-containing bifunctional or higher (meth)acrylate compound Cyanuric acid triacrylate (A9300 manufactured by Shinnakamura Chemical Industry Co., Ltd.), cresol novolac type epoxy resin (N-695 manufactured by DIC Co., Ltd.) and phenol as epoxy resin as a thermosetting component Novolac type epoxy resin (RE-306 manufactured by Nippon Kayaku Co., Ltd.), Omnirad 907 manufactured by IGM Resins Co., Ltd. as a photopolymerization initiator, DETX-S manufactured by Nippon Kayaku Co., Ltd., and Daido Chemical Industry Co., Ltd. EAB manufactured by the company, crystalline silica as other inorganic fillers (manufactured by Unimin Corporation, Imsil A8), dipentaerythritol 6 as a (meth)acrylate compound with no isocyanuric ring and more than two functions Acrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.), FASTOGEN GREEN S manufactured by DIC Co., Ltd. as a colorant, and carbitol acetate and petroleum solvents (manufactured by Showa Chemical Industry Co., Ltd.) as an organic solvent The SOLVESSO150) was blended in the ratio (parts by mass) shown in Table 1 below, pre-mixed with a mixer, and kneaded with a three-roll mixer to prepare a photosensitive resin composition.

Examples 1-2 to 1-12 and Comparative Examples 1-1 to 1-3 Except that the composition of the photosensitive resin composition was changed as described in Table 1, the photosensitive resin composition was prepared in the same manner as in Example 1-1.

In addition, the details of each component in Table 1 are as follows. (1) Resin containing carboxyl group ･Painting A～D (all used as the mixing amount of paint) (2) Talc ･LMP-100 Talc: manufactured by Fuji Talc Co., Ltd. (3) (Meth) acrylate having two or more functions with isocyanuric acid ring ･A9300: manufactured by Shinnakamura Chemical Industry Co., Ltd., ethoxylated tris(meth)acrylate isocyanurate ･A9300-CL: manufactured by Shinnakamura Chemical Industry Co., Ltd., caprolactone modified ethoxylated tri(meth)acrylate isocyanurate ･M-215: manufactured by Toagosei Co., Ltd., ethoxylated isocyanuric acid di(meth)acrylate (4) Epoxy resin ･N695: manufactured by DIC Co., Ltd., cresol novolac epoxy resin ･RE-306: Nippon Kayaku Co., Ltd., phenol novolac type epoxy resin ･JER834: manufactured by Mitsubishi Chemical Co., Ltd., bisphenol A epoxy resin ･TEPIC-S: Nissan Chemical Industry Co., Ltd., triazine epoxy resin (5) Photopolymerization initiator ･Omnirad 907: 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone manufactured by IGM Resins ･Omnirad TPO: 2,4,6-trimethylbenzyl diphenyl phosphine oxide manufactured by IGM Resins ･Kaya Cure DETX-S: 2,4-Diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd. ･EAB: 4,4’-Diethylaminobenzophenone manufactured by Datong Chemical Industry Co., Ltd. (6) Other inorganic fillers ･Imsil A8: manufactured by Unimin Corporation, crystalline silica ･Adma fineSO-C5: manufactured by Admatechs Co., Ltd., spherical silica ･A-26: manufactured by Sumitomo Chemical Co., Ltd., alumina ･B-30: manufactured by Sakai Chemical Industry Co., Ltd., barium sulfate (7) Bifunctional or higher (meth)acrylate without isocyanuric acid ring ･Kaya Cure DPHA: made by Nippon Kayaku Co., Ltd., dipentaerythritol hexa(meth)acrylate ･M-350: manufactured by Toagosei Co., Ltd., ethoxylated trimethylolpropane tri(meth)acrylate (8) Coloring agent ･FASTOGEN GREEN S: manufactured by DIC Co., Ltd. (9) Organic solvent ･SOLVESSO150: manufactured by Showa Chemical Industry Co., Ltd.

Example 2-1 <Preparation of two-component photosensitive resin composition> The carboxyl-containing resin obtained as described above was painted A, LMP-100 talc manufactured by Fuji Talc Co., Ltd., Omnirad 907 manufactured by IGM Resins Co., Ltd. as a photopolymerization initiator, and DETX- manufactured by Nippon Kayaku Co., Ltd. S and EAB manufactured by Datong Chemical Industry Co., Ltd., crystalline silica (Imsil A8 manufactured by Unimin Corporation) as other inorganic fillers, and (methyl) ) Dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.) as an acrylate compound, FASTOGEN GREEN S manufactured by DIC Co., Ltd. as a colorant, carbitol acetate as an organic solvent, and petroleum-based The solvent (SOLVESSO150 manufactured by Showa Chemical Industry Co., Ltd.) was blended in a ratio (parts by mass) as shown in Table 2 below, pre-mixed with a stirrer, and kneaded with a three-roll mixer to prepare the first composition. Ethoxylated isocyanurate triacrylate (A9300 manufactured by Shinnakamura Chemical Industry Co., Ltd.), which is a (meth)acrylate compound having an isocyanurate ring with two or more functions, is used as thermosetting The cresol novolac type epoxy resin (N-695 manufactured by DIC Co., Ltd.) and the phenol novolak type epoxy resin (RE-306 manufactured by Nippon Kayaku Co., Ltd.) are the same as the organic The carbitol acetate of the solvent and the petroleum solvent (Solvesso150 manufactured by Showa Chemical Industry Co., Ltd.) are blended in the proportions (parts by mass) shown in Table 2 below. After pre-mixing with a mixer, a 3-roll mixer After kneading, the second composition is prepared. A two-component photosensitive resin composition composed of the first composition and the second composition is obtained. After that, the first composition and the second composition are mixed and stirred until they are uniform.

Examples 2-2 to 2-14 and Comparative Examples 2-1 to 2-3 Except having changed the composition of the first composition and the second composition as described in Table 2, the same procedure as in Example 2-1 was carried out to prepare a two-component photosensitive resin composition. After that, the first composition and the second composition are mixed and stirred until they are uniform.

Example 3-1 <Preparation of photosensitive resin composition> The carboxyl group-containing resin varnish A obtained as described above, synthetic mica MK-100 manufactured by Katakura Coop Agri Co., Ltd., and ethoxylate as a bifunctional or higher (meth)acrylate compound having an isocyanuric acid ring Alkylated isocyanuric acid triacrylate (A9300 manufactured by Shinnakamura Chemical Industry Co., Ltd.), cresol novolac type epoxy resin (N-695 manufactured by DIC Co., Ltd.) as an epoxy resin as a thermosetting component ), Omnirad TPO manufactured by IGM Resins as a photopolymerization initiator and DETX-S manufactured by Nippon Kayaku Co., Ltd., spherical silica as other inorganic fillers (Adma fineSO- manufactured by Admatechs Co., Ltd.) C5) Dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.) as a (meth)acrylate compound with more than two functions without an isocyanuric acid ring, DIC Co., Ltd. as a colorant FASTOGEN GREEN S is prepared and blended with carbitol acetate as an organic solvent in the proportions (parts by mass) shown in Table 1 below. After pre-mixing with a mixer, it is kneaded with a 3-roller mixer to prepare photosensitivity. Resin composition.

Examples 3-2 to 3-7 and Comparative Examples 3-1 to 3-3 Except that the composition of the photosensitive resin composition was changed as described in Table 3, a photosensitive resin composition was prepared in the same manner as in Example 3-1.

And the details of each component in Table 3 are as follows. And for the duplicates in Table 1, the description will be omitted. (2) Mica･MK-100: manufactured by Katakura Coop Agri Co., Ltd., synthetic mica, KAl ₂ (AlSi ₃ O ₁₀ )F ₂ , with an average particle size of 3.4 μm ･M-HF: manufactured by Repko Co., Ltd., natural mica, KAl ₂ (AlSi ₃ O ₁₀ )(OH) ₂ , average particle size 4μm

Example 4-1 <Preparation of two-component photosensitive resin composition> The carboxyl-containing resin obtained as described above was painted A, MK-100 mica manufactured by Katakura Coop Agri Co., Ltd., Omnirad TPO manufactured by IGM Resins Co., Ltd. as a photopolymerization initiator, and DETX- manufactured by Nippon Kayaku Co., Ltd. S. Spherical silica (Adma fineSO-C5, manufactured by Admatechs Co., Ltd.) as other inorganic fillers, and dipentaerythritol as a (meth)acrylate compound that has no isocyanuric ring and is bifunctional or higher Hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.), FASTOGEN GREEN S manufactured by DIC Co., Ltd. as a colorant, and carbitol acetate as an organic solvent are in the ratio shown in Table 4 below (parts by mass) ) It is blended, and after pre-mixing with a mixer, it is kneaded with a three-roll mixer to prepare the first composition. Ethoxylated isocyanurate triacrylate (A9300 manufactured by Shinnakamura Chemical Industry Co., Ltd.), which is a (meth)acrylate compound having an isocyanuric ring and more than two functions, is used as thermosetting The cresol novolac epoxy resin (N-695 manufactured by DIC Co., Ltd.), which is an epoxy resin, is blended with carbitol acetate as an organic solvent in the ratio (parts by mass) shown in Table 4 below. , After pre-mixing with a mixer, kneading with a three-roll mixer to prepare the second composition. A two-component photosensitive resin composition composed of the first composition and the second composition was obtained. After that, the first composition and the second composition are mixed and stirred until they are uniform.

<Preparation of Evaluation Board> The resin compositions obtained from the above-mentioned Examples and Comparative Examples (for Examples 2-1 to 2-14, Comparative Examples 2-1 to 2-3, and Examples 4-1 to 4-9) And Comparative Examples 4-1 to 4-3 are mixtures of the first resin composition and the second resin composition). It was coated on a circuit pattern substrate with a copper thickness of 35μm by screen printing, and dried at 80°C for 30 minutes. , Cooling to room temperature, forming a resin layer with a thickness of 20 μm. For the resin layer, an exposure device equipped with a high-pressure mercury lamp (short arc lamp) was used to perform solid exposure with an optimal exposure amount, and then a 1wt% sodium carbonate aqueous solution at 30°C was developed for 60 seconds under a spray pressure of 0.2MPa. For the substrate, under the condition of a cumulative exposure amount of 1000 mJ/cm ² in a UV conveyor furnace, after irradiating ultraviolet rays, the resin layer is cured after being heated at 160°C for 60 minutes.

＜Solder heat resistance＞ After coating the rosin-based flux on the evaluation substrate prepared as described above, it was immersed twice in a solder bath at 260°C for 30 seconds. Next, the appearance after washing with flux was observed visually with modified alcohol, and evaluated based on the following evaluation criteria. The evaluation results are summarized in Tables 1 to 4. (Assessment criteria) ○: Even if the immersion in the solder tank was performed, peeling of the cured resin layer was not observed. △: After immersion in the solder tank, peeling of the cured resin layer was slightly observed. ×: After immersion in the solder tank, significant peeling of the cured resin layer was observed.

＜Cold and heat cycle resistance＞ On a substrate with a copper pattern of 2 mm, each resin composition obtained in the above-mentioned Examples and Comparative Examples was screen-printed to coat the entire surface, dried at 80°C for 30 minutes, and then cooled to room temperature to produce a form 17 evaluation boards with 3mm square resist pattern. The evaluation substrate was placed in a thermal cycler that circulated the temperature between -65°C and 150°C, and TCT (Thermal Cycle Test) was performed. After that, the appearance at 1,000 cycles was observed, the number of cracks was calculated, and the evaluation was performed based on the following evaluation criteria. The evaluation results are summarized in Tables 1 to 4. And the value "68" in the denominator represents the 4 corners (4) x 17 of the 68 corners of the 3mm square resist pattern, and the value "30" in the numerator represents the number of cracks. (Assessment criteria) ◎: Below 20/68 ○: 21/68 or more and 30/68 or less △: more than 31/68 and less than 40/68 ×: 41/68 or more

<Adhesion reduction prevention property> The evaluation substrate produced as described above was heated at 150°C for 2000 hours using a hot air circulation type drying oven DN610 manufactured by Yamato Scientific Co., Ltd. After that, 100 flaws were made ^{on a square of 1 mm 2} using an automatic crosscut tester No. 807-KS2 manufactured by Coating Tester Co., Ltd. on each evaluation substrate. Then, the peeling of the resin layer was confirmed by tape peeling, and it was evaluated based on the following evaluation criteria. The evaluation results are summarized in Tables 1 to 4. (Evaluation criteria) ◎: Peeling, no defects 〇: Peeling, the number of defects is 1 or more and 15 or less △: Peeling, the number of defects is more than 15 and 35 or less ×: There is peeling, the number of defects is more than 35 One and less than 65 ××: There is peeling, and the number of defects exceeds 65

It can be seen from the examples that the photosensitive resin composition of the present invention can make any of heat resistance, adhesion drop prevention properties, and cold and heat cycle resistance significantly good. In addition, it has been found that by using the photosensitive resin composition as a two-component type, it is possible to improve the prevention of adhesion drop and the resistance to cold and heat cycles.

Claims (12)

A photosensitive resin composition characterized by containing: Resins containing carboxyl groups; At least any one of talc and mica; (Meth)acrylates having two or more functionalities with isocyanuric acid ring; Epoxy resin; and Photopolymerization initiator. The photosensitive resin composition according to claim 1, wherein at least one of a novolak type carboxyl group-containing resin and a bisphenol type carboxyl group-containing resin is contained as the carboxyl group-containing resin. According to claim 1 or 2, the photosensitive resin composition contains at least any one of silicon oxide and aluminum oxide. The photosensitive resin composition according to any one of claims 1 to 3, which contains a (meth)acrylate that does not have an isocyanuric ring and is bifunctional or higher. The photosensitive resin composition according to any one of claims 1 to 4, which contains fluorine-containing mica as the mica. A two-component photosensitive resin composition, which is a two-component photosensitive resin composition composed of a first composition and a second composition, and is characterized by: The aforementioned first composition contains a carboxyl group-containing resin and a photopolymerization initiator; The aforementioned second composition contains epoxy resin; At least any one of the first composition and the second composition contains at least any one of talc and mica; and At least any one of the said 1st composition and the said 2nd composition contains the (meth)acrylate more than bifunctional which has an isocyanuric acid ring. The two-component photosensitive resin composition of claim 6, wherein the first composition contains at least any one of talc and mica. According to claim 6 or 7, the two-component photosensitive resin composition, wherein the second composition contains a (meth)acrylate having an isocyanuric ring-containing bifunctional or more functional (meth)acrylate. The two-component photosensitive resin composition according to any one of claims 6 to 8, wherein the first composition contains at least any one of silicon oxide and alumina. The two-component photosensitive resin composition according to any one of claims 6 to 9, wherein the first composition contains a (meth)acrylate that does not have an isocyanuric ring and is bifunctional or higher. A dry film characterized by: Membrane; and A resin layer obtained by coating the photosensitive resin composition according to any one of claims 1 to 5 or the two-liquid photosensitive resin composition according to any one of claims 6 to 10 on a film and drying. A printed wiring board characterized by having a photosensitive resin composition according to any one of claims 1 to 5, a two-component photosensitive resin composition according to any one of claims 6 to 10, or The resin layer of the dry film of 11 is cured and the cured product is obtained.