WO2017170959A1 - Curable resin composition, dry film, cured product and printed wiring board - Google Patents

Curable resin composition, dry film, cured product and printed wiring board Download PDF

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WO2017170959A1
WO2017170959A1 PCT/JP2017/013454 JP2017013454W WO2017170959A1 WO 2017170959 A1 WO2017170959 A1 WO 2017170959A1 JP 2017013454 W JP2017013454 W JP 2017013454W WO 2017170959 A1 WO2017170959 A1 WO 2017170959A1
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group
resin
resin composition
curable resin
epoxy
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PCT/JP2017/013454
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French (fr)
Japanese (ja)
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岡田 和也
千穂 植田
健志 依田
信人 伊藤
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太陽インキ製造株式会社
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04Acids; Metal salts or ammonium salts thereof
    • C08F220/06Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/26Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28Chemically modified polycondensates
    • C08G8/30Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/075Silicon-containing compounds
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/22Secondary treatment of printed circuits
    • H05K3/28Applying non-metallic protective coatings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/14Polysiloxanes containing silicon bound to oxygen-containing groups

Abstract

Provided are: a curable resin composition which is capable of providing a cured product that has excellent crack resistance and insulation reliability; a dry film which has a resin layer obtained from the composition; a cured product of the composition or the resin layer of the dry film; and a printed wiring board which comprises the cured product. A curable resin composition which is characterized by containing (A) a carboxyl group-containing resin and (B) an epoxy resin having a silsesquioxane skeleton; and the like.

Description

Curable resin composition, a dry film, the cured product and a printed wiring board

The present invention is a curable resin composition, a dry film, a cured product and a printed wiring board.

Conventionally, solder resist of the printed wiring board, an interlayer insulating layer, as a material for forming a permanent film such as a cover lay, for example, Patent Document 1, a reaction product of a novolak type epoxy compound and an unsaturated monocarboxylic acids, polybasic acid anhydride and an active energy ray curable resin obtained by reacting, a photopolymerization initiator, a composition containing a photopolymerizable monomer and an epoxy resin is disclosed.

In recent years, with the rapid progress of semiconductor parts, electronic equipment miniaturization, high performance, they tend to be multi-functional. Size of the semiconductor package to follow this trend, the number of pins has been put into practical use.
Specifically, QFP (quad flat pack package), SOP on behalf of IC package called (Small Outline Package) or the like, BGA (ball grid array), CSP (Chip Scale Package) or the like IC package called is being used. In recent years, as an IC package that is further densified, FC-BGA (flip chip ball grid array) has been practically.
Such IC package printed wiring board used in (also referred to as a package substrate.) In, SRO (Solder Resist Opening) pitch is narrow, because they are formed close to each other, short circuit and crosstalk noise occurs between SRO fear is increased to or. Also, a solder resist formed between SRO consists cracks tend to occur to become narrower thinner. Therefore, the permanent coating such as a solder resist for use in the package substrate, long-term high reliability, in particular high crack resistance and high insulation reliability is required. In particular, increases in density in the future of the package substrate, the reliability requirements are considered further enhanced.

Conventionally, as a resist composition which can be applied as a solder resist of the package substrate, for example, Patent Document 2, a polyfunctional monomer having organopolysiloxane having an epoxy group-containing organic group, phenol novolac having an acryloyl group, an optical functional group and / or diluent comprising a polyfunctional monomer having a photofunctional group and a terminal functional group, and a photosensitive resin composition containing a photopolymerization initiator is disclosed.

JP-A-61-243869 JP JP 2001-209183 JP

However, in the curable resin composition described in Patent Document 1, it can not be obtained a high degree of crack resistance and high insulation reliability.
On the other hand, in the photosensitive resin composition described in Patent Document 2, because of the use of phenolic novolac having an acryloyl group, it is necessary to increase the curing temperature, adhesion to a printed circuit board is lowered. Therefore, it is difficult to obtain crack resistance.
That is, in the permanent coating of the solder resist and the like used in the conventional package board, there is room for improvement in crack resistance and insulation reliability.

It is an object of the present invention, the curable resin composition capable of obtaining a cured product excellent in crack resistance and insulation reliability, a dry film having a resin layer obtained from the composition, the composition or of the dry film the cured product of the resin layer, and to provide a printed wiring board having a cured product.

The present inventors have a result of intensive studies in view of the above, and a carboxyl group-containing resin, by blending an epoxy resin having a silsesquioxane skeleton, can solve the above problems, thereby completing the present invention It was. Further, as the carboxyl group-containing resin, by using a carboxyl group-containing resin having a structure obtained compound by alkylene oxide modified with two or more phenolic hydroxyl groups in one molecule, more heat resistance and insulation reliability It can be improved.

That is, the curable resin composition of the present invention is characterized by containing (A) a carboxyl resin, and a epoxy resin having a (B) silsesquioxane skeleton.

The curable resin composition of the present invention preferably further contains (C) surface treated inorganic filler.

The curable resin composition of the present invention, the (A) a carboxyl group-containing resin preferably has a structure represented by the following general formula (1).

Figure JPOXMLDOC01-appb-I000004
(Wherein, R 1 ~ R 4 represents a hydrogen atom or an alkyl group independently, k represents any value of 0.3 to 10.)

The curable resin composition of the present invention, the (A) a carboxyl group-containing resin preferably has a structure represented by the following general formula (2).

Figure JPOXMLDOC01-appb-I000005
(Wherein, R 5 ~ R 7 each independently represent a hydrogen atom or an alkyl group, Z is represents an acid anhydride residue, m represents any value of 0.3 to 10.)

The curable resin composition of the present invention, the epoxy resin (B) having a silsesquioxane skeleton preferably has a structure represented by the following general formula (3).

Figure JPOXMLDOC01-appb-I000006
(Wherein, R 8 ~ R 11 are each independently a group or an organic group having an SiO bond, at least one of R 8 ~ R 11 is a group having an epoxy group.)

Dry film of the present invention, the curable resin composition, applied to the film, it is characterized in that it has a resin layer obtained by drying.

The cured product of the present invention, the resin layer of the curable resin composition or the dry film, is characterized in that obtained by curing.

Printed circuit board of the present invention is characterized by having the cured product.

According to the present invention, crack resistance and insulation reliability excellent curable resin composition cured product can be obtained, the dry film, the composition or the resin of the dry film having a resin layer obtained from the composition curing of the layer, and can provide a printed wiring board having a cured product.

The curable resin composition of the present invention is characterized by containing (A) a carboxyl resin, and a epoxy resin having a (B) silsesquioxane skeleton.

The curable resin composition of the present invention contains an epoxy resin having a carboxyl group-containing resin and silsesquioxane skeleton, the resulting cured product, the glass transition temperature (Tg) of higher coefficient of linear expansion (CTEarufa1, [alpha] 2) is low, the elastic modulus at high temperature (E) is high. Therefore, the flow resistance of the cured product can be suppressed to reduce the stress generated at high temperatures, it is excellent in heat resistance. In other words, the cured product of the present invention, the crosslinking density is high, it can be said that those not causing little change in physical properties at high temperatures.
Further, the curable resin composition of the present invention by containing an epoxy resin having a silsesquioxane skeleton, to suppress warpage during curing, it is possible to suppress the printed circuit board inside the generated stress.
Furthermore the curable resin composition of the present invention contains an epoxy resin having a carboxyl group-containing resin and a silsesquioxane skeleton, improves curability at low temperatures (reaction rate), the copper circuit by the high temperature treatment suppressing oxidation, it is possible to maintain the adhesion between the cured product and a printed wiring board.
Further, the cured product of the present invention, since the high elastic modulus at high temperature, the crosslinking density is high, water absorption is considered to be low.
Although detailed mechanism is not clear, such a heat resistance, low warping property, low-temperature curability, based on the low water absorption, the cured product of the curable resin composition of the present invention is considered excellent crack resistance and insulation reliability It is. Further, as described later, since a small maximum value of Tanδ in the temperature range of 25 ~ 300 ° C. of the cured product, it is considered possible to obtain a stable crack resistance.
Further, according to the curable resin composition of the present invention, it is also possible to obtain a cured product excellent in resolution.

The following describes each component of the curable resin composition of the present invention. In the present specification, the (meth) acrylate, acrylate, a term which collectively methacrylate and mixtures thereof, are the same for other similar expression.

[(A) a carboxyl group-containing resin]
(A) a carboxyl group-containing resin is polymerized or (B) is a component for curing by crosslinking with the epoxy resin can be an alkali-soluble by being included carboxyl group. The use in view of the photocurable and development resistance, in addition to the carboxyl group, it preferably has an ethylenically unsaturated group in the molecule, only the carboxyl group-containing resin having no ethylenically unsaturated group it may be. The ethylenically unsaturated groups, those derived from acrylic acid or methacrylic acid or their derivatives are preferred. Among the carboxyl group-containing resin, carboxyl group-containing resin having a copolymerization structure, carboxyl group-containing resin having a urethane structure, a carboxyl group-containing resin for the epoxy resin as a starting material, the carboxyl group-containing resin to the phenolic compound and the starting material preferable. Specific examples of the carboxyl group-containing resin include compounds as listed below (either oligomeric or polymeric).

(1) bifunctional or higher-functional epoxy resin (meth) reacting the acrylic acid, phthalic anhydride to a hydroxyl group present on the side chain, tetrahydrophthalic anhydride, dibasic anhydride such as hexahydrophthalic anhydride the addition of so carboxyl group-containing photosensitive resin. Here, it is preferable difunctional or higher-functional epoxy resin is a solid.

(2) 2 hydroxyl functional epoxy resins, more polyfunctional epoxy resins epoxidized with epichlorohydrin, (meth) reacting the acrylic acid and the resulting hydroxyl group to a dibasic acid anhydride added was carboxyl group containing photosensitive resin. Here, it is preferable that the bifunctional epoxy resin is a solid.

(3) an epoxy compound having two or more epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl groups in the molecule, such as (meth) acrylic acid- by reacting a saturated group-containing monocarboxylic acid, with respect to alcoholic hydroxyl group of the resulting reaction product, maleic acid anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, multi such as anhydrous adipic acid carboxyl group-containing photosensitive resin obtained by reacting a dibasic acid anhydride.

(4) bisphenol A, bisphenol F, bisphenol S, novolak phenolic resins, poly -p- hydroxystyrene, condensation products of a naphthol and an aldehyde, 2 or more in one molecule of the condensate of dihydroxynaphthalene and an aldehyde a compound having a phenolic hydroxyl group, ethylene oxide, the reaction product obtained by reacting an alkylene oxide such as propylene oxide, is reacted with (meth) unsaturated group containing monocarboxylic acids such as acrylic acid, obtained reaction carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride to the product.

(5) the compound with ethylene carbonate, the reaction product obtained by reacting a cyclic carbonate compound such as propylene carbonate having two or more phenolic hydroxyl groups in one molecule is reacted with an unsaturated group-containing monocarboxylic acid , resulting reaction product polybasic acid anhydride carboxyl group-containing photosensitive resin obtained by reacting.

(6) aliphatic diisocyanate, branched aliphatic diisocyanates, cycloaliphatic diisocyanates, a diisocyanate compound such as an aromatic diisocyanate, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A-based alkylene oxide adducts diols, phenolic hydroxyl groups and at the end of the urethane resin by polyaddition reaction of compounds of the diol compound having an alcoholic hydroxyl group, obtained by reacting an acid anhydride terminal carboxyl group-containing urethane resin.

(7) a diisocyanate and, dimethylolpropionic acid, and carboxyl group-containing dialcohol compounds such dimethylol butyric, during polyaddition reaction synthesis of the carboxyl group-containing urethane resin according to the diol compound, molecules such as hydroxyalkyl (meth) acrylate one hydroxyl group and a compound was added with one or more (meth) acryloyl groups, terminal (meth) acrylated carboxyl group-containing urethane resin in the.

(8) a diisocyanate, and a carboxyl group-containing dialcohol compound, during the synthesis of the carboxyl group-containing urethane resin by polyaddition reaction of a diol compound, an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate in the molecule 1 one of the isocyanate groups and compounds were added with one or more (meth) acryloyl groups, terminal (meth) acrylated carboxyl group-containing urethane resin.

(9) (meth) unsaturated carboxylic acids such as acrylic acid, styrene, alpha-methyl styrene, lower alkyl (meth) acrylate, carboxyl group-containing photosensitive obtained by copolymerization of the unsaturated group-containing compounds such as isobutylene resin.

(10) a polyfunctional oxetane resins, adipic acid, phthalic acid, by reacting a dicarboxylic acid such as hexahydrophthalic acid, the primary hydroxyl groups resulting, dibasic acid carboxyl group-containing polyester resin anhydride was allowed to addition.

(11) described above (1) to (10) to one of the carboxyl group-containing resin, a cyclic ether group and (meth) carboxyl group-containing photosensitive resin obtained by adding a compound having an acryloyl group in one molecule.

Examples of the carboxyl group-containing resin, the (1), (4), (5) and the carboxyl group-containing resin is preferably from (9), heat resistance of the cured product from the standpoint of improving (glass transition temperature) (1), (4), preferably a carboxyl group-containing resin (5). Among them from the viewpoints of insulation reliability, (4), and more preferably a carboxyl group-containing resin (5). Furthermore, the (4), (5) as in, it can be preferably used a carboxyl group-containing resin having the structure represented by the following general formula (1).

Figure JPOXMLDOC01-appb-I000007
(Wherein, R 1 ~ R 4 represents a hydrogen atom or an alkyl group independently, k represents any value of 0.3 to 10.)

The alkyl group can take R 1 ~ R 4, preferably an alkyl group having 1 to 20 carbon atoms.

Also, the (4), (5) as in, it can be preferably used a carboxyl group-containing resin having the structure represented by the following general formula (2).

Figure JPOXMLDOC01-appb-I000008
(Wherein, R 5 ~ R 7 each independently represent a hydrogen atom or an alkyl group, Z is represents an acid anhydride residue, m represents any value of 0.3 to 10.)

The alkyl group can take R 5 ~ R 7 is preferably an alkyl group having 1 to 20 carbon atoms.

The acid anhydride residue Z can take, an acid anhydride residue derived from a carboxylic acid anhydride shown below, for example, tetrahydrophthalic anhydride, maleic anhydride, succinic anhydride, trimellitic acid anhydride include acid anhydride residues such as pyromellitic anhydride.

As the general formula carboxyl group-containing resin having a structure represented by the structure and the general formula represented by (1) (2), as described above (4) or (5), two in one molecule It includes compounds and the reaction products of an alkylene oxide or cyclic carbonate compound, carboxyl group-containing resin which is a reaction product of a carboxylic acid and a polybasic acid anhydride having an ethylenically unsaturated group having more phenolic hydroxyl groups . Incidentally, the compound and reaction products of an alkylene oxide or cyclic carbonate compound having two or more phenolic hydroxyl groups wherein in one molecule, not only carboxylic acid having an ethylenically unsaturated group, saturated aliphatic monocarboxylic after reacting at least one of acids and aromatic monocarboxylic acids, carboxylic acids and polybasic acid anhydrides may be reacted with an ethylenically unsaturated group.

The compound wherein in one molecule having two or more phenolic hydroxyl groups, catechol, resorcinol, hydroquinone, dihydroxy toluene, naphthalene diol, t- butyl catechol, t- butyl hydroquinone, pyrogallol, phloroglucinol, bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl ether, phenolphthalein, condensates of the novolak type phenolic resins, phenols and aromatic aldehydes having a phenolic hydroxyl group, poly -p- hydroxystyrene, 1-naphthol, or condensation products such as 2-naphthol and an aldehyde (i.e. naphthol novolak resins), 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 2, 3 -, 2,6-, 2,7-condensates of dihydroxynaphthalene and an aldehyde, condensation products of mono-naphthol and the dihydroxynaphthalene and an aldehyde, condensation products of mono- or dihydroxy naphthalene and xylylene glycols, mono or the like can be given. adduct of dihydroxynaphthalene and the diene compound is not limited thereto. These compounds having a phenolic hydroxyl group may be used alone or in admixture of two or more.

The compound having a phenolic hydroxyl group as described above, the hydrocarbon backbone linked to the phenolic ring on or phenol ring, a functional group containing a halogen atom, an oxygen, nitrogen, sulfur, etc., for example, a halogen group, an ether group, an ester group includes a carbonyl group, hydroxyl group, aldehyde group, amino group, amido group, nitrile group, a nitro group, a thiol group, those having a hetero-aromatic group such as a thioether group, other pyridyl group and imidazole group.

Preferred among the compounds having these phenolic hydroxyl groups, a compound having three or more phenolic hydroxyl groups per molecule, more preferably, an aromatic having novolak phenol resin, a phenol and a phenolic hydroxyl group condensation products of an aldehyde and the like.

Addition rate of the alkylene oxide to the compound having the phenolic hydroxyl group, a phenolic hydroxyl group per equivalent of the compound having a phenolic hydroxyl group, is 0.3-10.0 mol preferred. For 0.3 mol or more, in the photosensitive carboxy group-containing resin obtained photocurable becomes good. Also, in the case of 10.0 mol, photocurable and thermosetting it becomes good.

The addition reaction of the alkylene oxide to the compound having a phenolic hydroxyl group is preferably carried out at room temperature ~ 250 ° C.. As the reaction solvent, benzene, toluene, xylene, tetramethyl benzene, n- hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, octane, methyl isobutyl ketone, diisopropyl ether or the like is preferably used. These organic solvents may be used alone or in admixture of two or more.

The reaction catalyst, potassium carbonate, sodium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, alkali metal compounds such as barium hydroxide, tertiary amines, imidazole compounds such as 2-ethyl-4-methylimidazole as triethylamine , phosphorus compounds such as triphenylphosphine, tetramethylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium halides, tetramethylammonium benzoate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, quaternary such as tetramethyl phosphonium hydroxide basic salt compounds, naphthenic acid, lauric acid, stearic acid, lithium oleate and Okutoen acid, chromium, zirconium, Potassium, such as metal salts of organic acids such as sodium is preferably used. These catalysts may be used alone or in admixture of two or more.

As the alkylene oxide, ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran and the like. The cyclic carbonate compound, can be used carbonate compounds conventionally known, for example, ethylene carbonate, propylene carbonate, butylene carbonate, are like 2,3 carbonate methacrylate, preferably 5-membered ring of ethylene carbonate, propylene carbonate It preferred in view of reactivity. Each of these alkylene oxide and a cyclic carbonate compound can be used alone or in admixture of two or more.

By reacting an unsaturated group-containing monocarboxylic acid in the reaction product obtained by reacting a compound having a phenolic hydroxyl group and an alkylene oxide or cyclic carbonate compound, it is possible to obtain a reaction product, upon its the reaction temperature in the esterification reaction can be carried out preferably 50 ~ 120 ° C., under a reduced pressure, normal pressure, the either reaction under pressure. In this esterification reaction, the unsaturated group-containing monocarboxylic acid, a photosensitive carboxyl resin obtained double bond equivalent of 300 ~ 800g / eq. It is desirable to become such additional amount.

As the reaction solvent, benzene, toluene, xylene, tetramethyl benzene, n- hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, octane, methyl isobutyl ketone, diisopropyl ether or the like is preferably used. These organic solvents may be used alone or in admixture of two or more.
The esterification catalyst, sulfuric acid, hydrochloric acid, phosphoric acid, boron fluoride, methanesulfonic acid, benzenesulfonic acid, p- toluenesulfonic acid, cation exchange resin or the like is used appropriately. Is preferably carried out in the presence of an esterification reaction of the polymerization inhibitor, the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol or the like is preferably used.

Examples typify the unsaturated group-containing monocarboxylic acids are acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, alpha-cyano cinnamic acid, beta-styryl acrylic acid, and the like beta-furfuryl acrylate . Here, in particular preferred are acrylic acid and methacrylic acid. These unsaturated group-containing monocarboxylic acids may be used alone or in admixture of two or more.

The reaction product of said reaction product with an unsaturated group-containing monocarboxylic acid, by reacting a polybasic acid anhydride, although carboxyl group-containing photosensitive resin (photosensitive prepolymer) is obtained in the reaction, the amount of the polybasic acid anhydride, the acid value of the carboxyl group-containing photosensitive resin to produce is preferably 20 ~ 200 mg KOH / g, more preferably additional amount such that 50 ~ 120mgKOH / g. The reaction is carried out in the presence or absence of an organic solvent which will be described later, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, the presence of a polymerization inhibitor pyrogallol, usually carried out at about 50 ~ 0.99 ° C.. In this case if necessary, a tertiary amine such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, 2-ethyl-4-imidazole compounds of methylimidazole, phosphorus compounds such as triphenylphosphine, naphthenic acid, lauric acid, stearic acid, lithium oleate and Okutoen acid, chromium, may be added zirconium, potassium, and metal salts of organic acids such as sodium as a catalyst. These catalysts may be used alone or in admixture of two or more.

Examples of the polybasic acid anhydride, methyl tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic acid, 3,6-tetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, tetrabromophthalic alicyclic dibasic acid anhydrides such as phthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, Pentadodeseniru succinic anhydride, phthalic anhydride, trimellitic anhydride aliphatic or aromatic dibasic or tribasic acid anhydride and the like, or biphenyltetracarboxylic acid dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic acid dianhydride , pyromellitic acid anhydride Aliphatic or aromatic tetrabasic acid dianhydride such as benzophenone tetracarboxylic acid dianhydride and the like, can be used one or two or more of them. Among these, alicyclic dibasic acid anhydride is particularly preferred.

(A) the acid value of the carboxyl group-containing resin is preferably 20 ~ 200mgKOH / g. When (A) the acid value of the carboxyl group-containing resin is 20 ~ 200mgKOH / g, it is easy to form a pattern of a cured product. More preferably 50 ~ 130mgKOH / g.

(A) The amount of the carboxyl group-containing resin is a curable resin composition the total amount excluding the solvent, for example, 15 to 60 mass%, preferably 20 to 60 mass%. 15 wt% or more, preferably it is possible to improve the coating strength by 20 mass% or more. The workability viscosity becomes appropriate is improved by 60 mass% or less. More preferably 30 to 50 mass%. (A) a carboxyl group-containing resin alone or may be used in combination of two or more.

[(B) an epoxy resin having a silsesquioxane skeleton]
(B) an epoxy resin (hereinafter, simply "epoxy resin (B)" also abbreviated) having a silsesquioxane skeleton as a silsesquioxane, i.e., obtained by hydrolyzing a trifunctional silane ( RSiO 1.5) a network polymer or polyhedral clusters having the structure of n, is not particularly limited as long as it is a compound having a group containing an epoxy group. Each silicon silsesquioxane is bound to the average 1.5 oxygen atoms and one hydrocarbon group.
Here, (B) epoxy resin is preferably an epoxy resin containing no halogen atom.

The epoxy resin (B) preferably has a silsesquioxane skeleton represented by the following general formula (3).

Figure JPOXMLDOC01-appb-I000009
(Wherein, R 8 ~ R 11 are each independently a group or an organic group having an SiO bond, at least one of R 8 ~ R 11 is a group having an epoxy group.) Here, the organic the group, refers to a group containing a carbon atom.

The structure of silsesquioxane is not particularly limited, and may be random structure, ladder structure, complete cage structure, the silsesquioxane known conventional construction, such as incomplete cage structure.

Examples of the group having a SiO bond R 8 ~ R 11 can be taken is not particularly limited, a group having an SiO bond and aliphatic structure, a group having an SiO bond and an aromatic skeleton, and a group having an SiO bond and heteroatoms and the like, it is preferable that the range of the following epoxy equivalent.

The organic group can take R 8 ~ R 11, not particularly limited, aliphatic group such as a methyl group, an aromatic group such as a phenyl group, an organic group having a hetero atom. Preferably an organic group having 1 to 30 carbon atoms, it is preferable that the range of the following epoxy equivalent.

At least one of R 8 ~ R 11 is a group having an epoxy group, as the group having a wherein epoxy group is not particularly limited, group or an organic group having an SiO bond may if it has an epoxy group .

(B) an epoxy equivalent of the epoxy resin, 100 ~ 400g / eq. It is preferably, 150 ~ 250g / eq. More preferably. 100g / eq. For more, storage stability is improved. 400g / eq. In the following cases, the cured product of the CTE (α1, α2) can be reduced.

(B) The amount of epoxy resin, (A) on a carboxyl group-containing resin 100 parts by weight, for example, 1 to 100 parts by weight, preferably 5 to 80 parts by mass, more preferably from 10 to 80 parts by weight, more preferably 10 to 60 parts by weight, particularly preferably 20 to 60 parts by mass, most preferably 25 to 60 parts by weight. If the amount of the epoxy resin (B) is at least 1 part by weight, further improved crack resistance and insulation reliability, is not more than 100 parts by weight, storage stability is improved.

((C) surface treated inorganic filler)
The curable resin composition of the present invention preferably contains an inorganic filler, and is the inorganic filler (C) surface treated inorganic filler (hereinafter referred to simply as "(C) an inorganic filler") it is more preferable. (C) by including an inorganic filler, crack resistance of the cured product is further improved.
Here, the surface treatment of the inorganic filler (C) refers to a process for improving the compatibility with the (A) a carboxyl group-containing resin or the epoxy resin (B).
(C) the surface treatment of the inorganic filler is not particularly limited, can be introduced surface treatment curable reactive groups on the surface of the inorganic filler is preferred.

The inorganic filler is not particularly limited, conventionally known fillers such as silica, crystalline silica, Noiburugu siliceous earth, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, can be used barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, an inorganic filler such as zinc oxide. Among them, silica is preferred, the surface area is small, since less likely to crack start point for stress is dispersed throughout, also because of excellent resolution, and is more preferably spherical silica.

(C) inorganic filler preferably has a (A) a carboxyl group-containing resin and (B) a surface a curable reactive group which reacts with at least one of the epoxy resin. Curable reactive group may be a photocurable reactive group with a thermosetting reactive group. The thermosetting reactive group, a hydroxyl group, a carboxyl group, an isocyanate group, an amino group, an imino group, an epoxy group, an oxetanyl group, a mercapto group, a methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group, an oxazoline group, etc. and the like. The photocurable reactive group, vinyl group, styryl group, a methacryl group, and an acrylic group. Among them, as the photocurable reactive group, methacryl group, acryl group, a vinyl group are preferable Examples of the thermosetting reactive group, an epoxy group is preferable. Further, it may have a (C) inorganic filler is 2 or more curing reaction group. (C) The inorganic filler, surface treated silica is preferred. The inclusion of surface treated silica, can be higher glass transition temperature.

(C) a method of introducing curable reactive groups on the surface of the inorganic filler is not particularly limited, may be introduced using known conventional methods, a surface treating agent having a curable reactive group, for example, a curable reactive group it may be treating the surface of the inorganic filler with a coupling agent having.

The surface treatment of the (C) inorganic filler, the surface treatment by the preferred coupling agent. As the coupling agent, silane coupling agent, titanium coupling agent, zirconium coupling agents, and aluminum coupling agents. Among these, silane coupling agents are preferred.

The silane coupling agent, (C) an inorganic filler, a silane coupling agent capable of introducing a curable reactive group. Examples of the silane coupling agent capable of introducing a thermosetting reactive group, a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having a mercapto group, a silane coupling having an isocyanate group agent. Among these silane coupling agents having an epoxy group is more preferable. Examples of the silane coupling agent capable of introducing a photocurable reactive groups, silane coupling agents having a vinyl group, a silane coupling agent having a styryl group, a silane coupling agent having a methacryl group, a silane coupling having an acrylic group agent is preferred, a silane coupling agent having a methacryl group are more preferable.

As the inorganic filler (C) having no curable reactive group, for example, inorganic fillers, and the like to the alumina surface treatment it is.

(C) inorganic filler only needs to be blended in the curable resin composition of the present invention in a state in which the surface treated, an inorganic filler and a surface treating agent of the surface-untreated formulated separately in the compositions inorganic filler may be surface treated, but it is preferably blended inorganic filler in advance surface treatment. By blending preliminarily surface-treated inorganic filler, it is possible to prevent deterioration such as crack resistance due to the surface treatment agent which has not been consumed in the remaining can surface treatment when were separately blended. Advance the case of surface treatment, it is preferable to blend a preliminary dispersion in a solvent or resin components of (C) an inorganic filler was pre-dispersed, the inorganic filler surface-treated with pre-dispersed in a solvent, the preliminary dispersion composition or incorporated into, it was thoroughly surface treated in pre-dispersing the inorganic filler surface-untreated in a solvent, it is more preferable to blend the preliminary dispersion to the composition.

In the curable resin composition of the present invention, an inorganic filler, the average particle diameter is 2μm or less is preferable because of excellent by crack resistance. More preferably, the 1μm or less. In the present specification, the average particle diameter is a value of D50 measured using a Microtrac particle size analyzer manufactured by Nikkiso Co..

The amount of the inorganic filler is preferably 20 to 80 wt% per total amount of the solid content of the curable resin composition, more preferably from 30 to 80 mass%, from 35 to 80 mass% A further preferred.

The curable resin composition of the present invention may be used in combination with inorganic filler not treated (C) and the inorganic filler, the surface. In that case, (C) an inorganic filler, the total amount per (C) an inorganic filler and a surface untreated inorganic filler, preferably at least 30 wt%, more preferably at least 50 mass%, 70 mass it is more preferably not less than%. The inorganic filler which has not been surface treated, it is preferably spherical silica.

(At least one kind of photopolymerization initiator and a photo base generator)
The curable resin composition of the present invention, in the case of a photocurable at least any one of the photopolymerization initiator and a photo base generating agent is preferably used. As the photopolymerization initiator, any known photopolymerization initiator as a photopolymerization initiator or photo-radical generator may be used any of those.

As the photopolymerization initiator, for example, bis - (2,6-dichlorobenzoyl) phenyl phosphine oxide, bis - (2,6-dichlorobenzoyl) -2,5-dimethylphenyl phosphine oxide, bis - (2, 6-dichlorobenzoyl) -4-propylphenyl phosphine oxide, bis - (2,6-dichlorobenzoyl) -1-naphthyl phosphine oxide, bis - (2,6-dimethoxybenzoyl) phenyl phosphine oxide, bis - ( 2,6-dimethoxybenzoyl) -2,4,4-trimethyl pentyl phosphine oxide, bis - (2,6-dimethoxybenzoyl) -2,5-dimethylphenyl phosphine oxide, bis - (2,4,6 trimethyl benzoyl) - phenyl phosphine oxide BASF Japan Ltd. IRGACURE 819) bisacylphosphine oxides, such as, 2,6-dimethoxybenzoyl diphenyl phosphine oxide, 2,6-dichlorobenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl phenyl phosphine methyl ester, 2-methylbenzoyl diphenylphosphine oxide, pivaloyl triphenylphosphine acid isopropyl ester, monoacyl phosphine oxide such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide (BASF Japan Ltd. IRGACURE TPO); 1-hydroxy - cyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) - phenyl] -2-hydroxy-2-methyl-1-flop Bread-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl - propionyl) - benzyl] phenyl} -2-methyl - propan-1-one, 2-hydroxy-2 - hydroxyacetophenone such as methyl-1-phenylpropane-1-one; benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n- propyl ether, benzoin isopropyl ether, benzoin ethers such as benzoin n- butyl ether; benzoin alkyl ethers; benzophenone, p- methyl benzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, benzophenones such as 4,4'-bis-diethylamino benzophenone; acetophenone, 2,2-dimethoxy - 2-phenyl acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloro acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1 - propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) - butanone-1,2 (dimethylamino) -2 - [(4-methylphenyl) methyl) -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-acetophenones of such as dimethyl aminoacetophenone; thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chloro-thioxanthone, 2,4-diisopropyl Thioxanthones such as isopropyl thioxanthone; anthraquinone, chloroanthraquinone, 2-methyl anthraquinone, 2-ethylanthraquinone, 2-tert-butyl anthraquinone, 1-chloro anthraquinone, 2-amyl anthraquinone, anthraquinones such as 2-aminoanthraquinone; acetophenone dimethyl ketal, ketal such as benzil dimethyl ketal; ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethyl benzoate, p- hydroxybenzoic acid esters of dimethylbenzoic acid ethyl ester and the like; 1,2-octane-dione, 1 - [4- (phenylthio) -, 2- (O-benzoyl oxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- carbazol-3-yl] -, 1- Oxime esters O- acetyloxime) and the like; bis (Ita5-2,4- cyclopentadiene-1-yl) - bis (2,6-difluoro-3-(1H-pyrrol-1-yl) phenyl) titanium, bis (cyclopentadienyl) - bis [2,6-difluoro-3- (2- (1-pill-1-yl) ethyl) phenyl] titanocene and titanium; phenyl disulfide 2-nitrofluorene, butyroin, anisole it can be mentioned in ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide and the like. The photopolymerization initiators may be used singly or may be used in combination of two or more kinds. Among these mono-acylphosphine oxides, oxime esters Preferably, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- carbazol -3 - yl] -, 1- (O- acetyloxime) is more preferable.

The amount of the photopolymerization initiator is preferably 0.5 to 20 parts by weight per 100 parts by mass of (A) a carboxyl group-containing resin. For more than 0.5 part by weight, the surface curability is improved, if more than 20 parts by weight, halation hardly occurs satisfactory resolution can be obtained.

Photobase generator, or the molecular structure by light irradiation of ultraviolet rays or visible light or the like is changed, or, by the molecule cleaved to produce one or more basic substances that can function as a catalyst for the thermosetting reaction it is a compound. As the basic substance, for example, secondary amines, tertiary amines.

As photobase generators, for example, alpha-aminoacetophenone compound, an oxime ester compound, N- formylated aromatic amino compound, N- acylated aromatic amino compounds, nitrobenzyl carbamate compounds include alkoxy oxybenzyl carbamate compounds . Of these, oxime ester compounds, preferably α- aminoacetophenone compound, more preferably an oxime ester compound, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- carbazol-3-yl] -, 1-(O-acetyl oxime) it is more preferable. The α- aminoacetophenone compound, particularly preferably those having two or more nitrogen atoms. Photobase generator may be used singly or may be used in combination of two or more kinds.

In addition, as the photobase generator include quaternary ammonium salts and the like.

Other photobase generator, WPBG-018 (trade name: 9-anthrylmethyl N, N'-diethylcarbamate), WPBG-027 (trade name: (E) -1- [3- (2-hydroxyphenyl) -2- propenoyl] piperidine), WPBG-082 (trade name: guanidinium2- (3-benzoylphenyl) propionate), WPBG-140 (trade name: 1- (anthraquinon-2-yl) ethyl imidazolecarboxylate) or the like can also be used.

In addition, some of the material of the photopolymerization initiator described above also functions as a photobase generator. The photopolymerization initiator which acts as a photobase generator, an oxime ester-based photopolymerization initiator and α- aminoacetophenone-based photopolymerization initiator.

The amount of the photobase generator is preferably 0.1 to 20 parts by weight per 100 parts by weight of (A) a carboxyl group-containing resin. For more than 0.1 part by weight, the surface curability is improved, if more than 20 parts by weight, halation hardly occurs satisfactory resolution can be obtained.

(Compound having an ethylenically unsaturated group)
The curable resin composition of the present invention, in the case of a photocurable, the compound having one or more ethylenically unsaturated groups in the molecule is preferably used. Examples of the compound having an ethylenically unsaturated group, can be used photopolymerizable oligomer which is a photosensitive monomer conventionally known, a photopolymerizable vinyl monomer and the like. Note that the compound having an ethylenically unsaturated group as referred to herein is assumed to have an ethylenically unsaturated group (A) a carboxyl group-containing resin and (C) a surface-treated inorganic filler is not included.

As the photopolymerizable oligomer, unsaturated polyester oligomers, and (meth) acrylate oligomer. The (meth) acrylate oligomer, phenol novolac epoxy (meth) acrylate, cresol novolak epoxy (meth) acrylate, epoxy (meth) acrylates such as bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meth ) acrylates, polyester (meth) acrylates, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate.

As the photopolymerizable vinyl monomers include those conventionally known, for example, styrene, chlorostyrene, alpha-styrene derivatives such as methyl styrene; vinyl acetate, vinyl esters such as vinyl butyrate or vinyl benzoate, vinyl isobutyl ether, vinyl - n- butyl ether, vinyl -t- butyl ether, vinyl -n- amyl ether, vinyl isoamyl ether, vinyl -n- octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl ether, vinyl ethers such as triethylene glycol monomethyl ether; acrylamide, methacrylamide, N- hydroxymethyl acrylamide, N- hydroxymethyl methacrylamide, N- methoxymethyl acrylamide, N- ethoxymethyl Accession Ruamido, (meth) acrylamides such as N- butoxymethyl acrylamide; triallyl isocyanurate, diallyl phthalate, allyl compounds such as diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, esters of (meth) acrylic acid such as phenoxyethyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol hydroxyalkyl (meth) acrylates such as tri (meth) acrylate; methoxyethyl (meth) acrylate, alkoxyalkyl such as ethoxyethyl (meth) acrylate Xylene alkylene glycol mono (meth) acrylate, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, alkylene polyol poly (meth) acrylates such as dipentaerythritol hexa (meth) acrylate diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxy trimethylolpropane triacrylate, polyoxyalkylene glycol poly (main, such as propoxylated trimethylolpropane tri (meth) acrylate ) Acrylates, poly (meth) acrylates such as hydroxypivalic acid neopentyl glycol ester di (meth) acrylate; tris [(meth) acryloxyethyl] like isocyanuric rate poly (meth) acrylates such as isocyanurates It is. These are in accordance with the required characteristics, either alone or may be used in combination of two or more.

The amount of the compound having an ethylenically unsaturated bond is preferably 3 to 40 parts by weight per 100 parts by weight of (A) a carboxyl group-containing resin. For more than 3 parts by weight, it improves the surface curability, the case of 40 parts by mass or less, halation can be suppressed. More preferably 5 to 30 parts by weight.

(Thermal curing catalyst)
The curable resin composition of the present invention preferably contains a thermal curing catalyst. Such thermal curing catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole 1- (2-cyanoethyl) -2-ethyl-4-imidazole derivatives methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy -N, N - dimethylbenzylamine, 4-methyl -N, N-amine compound of dimethylbenzylamine and the like, adipic acid dihydrazide, hydrazine compounds such as sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine and the like. Further, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl -S- triazine, 2-vinyl-2,4-diamino -S- triazine, 2-vinyl-4,6-diamino -S- triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxy can also be used acryloyloxyethyl -S- triazine isocyanuric acid adduct S- triazine derivatives such as preferably they tackifier combination of a compound also functions as thermal curing catalyst.

The amount of the thermal curing catalyst for the epoxy resin (B) 100 parts by weight, for example, 0.05 to 80 parts by mass, preferably 0.05 to 50 parts by weight, more preferably 0.05-40 parts by weight, more preferably 0.1 to 30 parts by weight.

(Curing agent)
The curable resin composition of the present invention may contain a curing agent. As the curing agent, a phenolic resin, polycarboxylic acids and their anhydrides, cyanate ester resin, an active ester resin, a maleimide compound, alicyclic olefin polymer and the like. Hardeners can be used alone or in combination of two or more of them.

Curing agent, (B) the ratio of the functional group capable heat curing reaction of epoxy groups in the thermosetting resin such as epoxy resin, the functional group in the curing agent which reacts with the functional groups, the curing agent it is preferably added in proportions such functional groups / thermosetting reaction becomes functional group (equivalent ratio) = 0.2 to 3 possible. By the above range, excellent balance of curability and storage stability.

(Coloring agent)
The curable resin composition of the present invention may contain a colorant. As the coloring agent, red, blue, green, yellow, black, it is possible to use a known coloring agent such as white, pigments, dyes, may be any of dye. However, it is preferred not to contain a halogen in terms of environmental impact load reduction and the human body.

Is not particularly limited amount of colorant with respect to (A) 100 parts by mass of the carboxyl group-containing resin is preferably 10 parts by mass or less, particularly well preferably in a proportion of 0.1 to 7 parts by weight.

(Organic solvent)
The curable resin composition of the present invention, preparation of the composition and, for the purpose of viscosity adjustment or the like upon application to the substrate or carrier film may contain an organic solvent. As the organic solvent, methyl ethyl ketone, ketones such as cyclohexanone; toluene, xylene, aromatic hydrocarbons such as tetramethyl benzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether , dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, glycol ethers such as tripropylene glycol monomethyl ether, ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, Buchirukarubi tall acetate, propylene glycol monomethyl ether acetate, Jipu Propylene glycol monomethyl ether acetate, esters such as propylene carbonate; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, and petroleum solvents such as solvent naphtha, organic solvents conventionally known can be used. These organic solvents may be used alone or in combination of two or more.

(Other optional ingredients)
Further, the curable resin composition of the present invention may contain other additives conventionally known in the field of electronic materials. Other additives, thermal polymerization inhibitor, an ultraviolet absorber, a silane coupling agent, plasticizer, flame retardant, antistatic agent, antioxidant, antibacterial and antifungal, anti-foaming agents, leveling agents, thickening agents, adhesion imparting agents, thixotropic agents, co-initiator, a sensitizer, a thermoplastic resin, an organic filler, releasing agent, surface treating agent, dispersant, dispersion aid, surface modifier, stabilizer , and a phosphor or the like.

The curable resin composition of the present invention, without impairing the effect of the present invention (B) may contain a thermosetting resin other than epoxy resin. The thermosetting resin was cured by heating may be a resin exhibiting electrical insulation properties, for example, (B) an epoxy compound other than the epoxy resin, oxetane compound, a melamine resin, can be a silicone resin is exemplified, these may be used in combination.

As the (B) thermosetting resin other than epoxy resin, a compound having a plurality of annular (thio) ether groups in the molecule. Compounds having a plurality of cyclic (thio) ether groups in the above molecules are 3,4 or 5-membered cyclic (thio) compound having a plurality of ether groups in the molecule, for example, a plurality of epoxy in the molecule compounds having a group, i.e., a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, i.e. polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, i.e. polyfunctional episulfide resins.
Examples of the polyfunctional epoxy compound, epoxidized vegetable oil; bisphenol A type epoxy resins; hydroquinone-type epoxy resins; bisphenol epoxy resins; thioether type epoxy resins; brominated epoxy resins; novolak-type epoxy resins; biphenol novolak type epoxy resin; bisphenol F type epoxy resins; hydrogenated bisphenol A type epoxy resin; glycidyl amine type epoxy resins; hydantoin type epoxy resins; alicyclic epoxy resins; trihydroxyphenyl methane type epoxy resins; alkylphenol type epoxy resin (e.g., bixylenol type epoxy resin) ; biphenol type epoxy resins; bisphenol S type epoxy resin; bisphenol A novolac type epoxy resin; tetraphenylolethane type epoxy resin; heterocyclic Epoxy resins having a silsesquioxane skeleton; wherein the epoxy resin; diglycidyl phthalate resin; tetraglycidyl xylenoyl yl ethane resins; triphenylmethane type epoxy resin, epoxy resins having a dicyclopentadiene skeleton; naphthalene group-containing epoxy resin of glycidyl methacrylate copolymer type epoxy resin; copolymer epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, epoxy-modified polybutadiene rubber derivative; but CTBN modified epoxy resins, but is not limited thereto. These epoxy resins may be used alone or in combination of two or more of them. In particular triphenylmethane type epoxy resin among these, novolac type epoxy resins, bisphenol epoxy resins, bixylenol type epoxy resin, biphenol type epoxy resin, biphenol novolak type epoxy resin, naphthalene type epoxy resins, or mixtures thereof, are preferred. (B) an epoxy resin having a silsesquioxane skeleton, by combination with other epoxy resins, it is possible to increase the glass transition temperature of the cured product.

The curable resin composition of the present invention preferably the maximum value of Tanδ in the temperature range of 25 ~ 300 ° C. of the cured product is less than 0.25. With such properties, also can be obtained a stable crack resistance as the temperature of the cured film becomes more Tg near or Tg.
In this specification, Tan?, Unless otherwise noted, the resin layer after drying of the resin composition, after irradiation with ultraviolet rays of about 500 mJ / cm 2, using a UV conveyer furnace further provided with a high-pressure mercury lamp after irradiation at an exposure dose of 1 J / cm 2, it means the properties of a cured product with a thickness of 40μm to obtain a resin layer was completely cured by heating 60 minutes at 160 ° C.. Further, the ultraviolet is an electromagnetic wave having a wavelength of 10 ~ 400 nm. Tan?, The value obtained by dividing the storage modulus loss modulus measured with a dynamic viscoelasticity measurement, i.e., the loss tangent (= loss modulus / storage modulus), Tan? Herein, frequency 1 Hz, it is based on the chart obtained by measuring to 25 ° C. ~ 300 ° C. under conditions of heating rate 5 ° C. / min.

Tanδ To (= loss modulus / storage modulus) to obtain a small cured product, decreases the loss modulus (viscous component), or increases the storage modulus (elasticity component), be performed both good, in other words, it may be as much as possible the elastic component than viscous component with a cured product in.
Means for the maximum value of Tanδ of less than 0.25 is not particularly limited.

The maximum value of Tanδ of less than 0.20, preferably 0.15 or less, especially is 0.13 or less is preferable because cracking resistance is further improved.

Also, by reducing the equivalent of the epoxy groups of the thermosetting component such as epoxy resin (B), also, the case of mixing a compound having an ethylenically unsaturated group, by or to the amount in a small amount , it is possible to reduce the Tanδ of the cured product. (B) equivalent of the epoxy group of the epoxy resin, 400 g / eq. That it is preferably less.

If a large maximum value of Tanδ of the cured product, but the cured product is viscous component is easy to move the physical properties of the cured product when exposed to high temperature changes significantly, the maximum value of Tanδ is there with a cured product of less than 0.25 if, property changes without moving little viscous component even at a high temperature state close to Tg of the cured product is small, occurrence of cracks can be suppressed more.

The curable resin composition of the present invention may be used as a liquid be used to dry a film. When used as a liquid, it may be two-component or even one pack.

Next, dry film of the present invention has on a carrier film, applying a curable resin composition of the present invention, a resin layer obtained by drying. In forming a dry film, first, in terms of the curable resin composition of the present invention was adjusted to a suitable viscosity by diluting with the organic solvent, a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater , reverse coater, transfer roll coater, a gravure coater, a spray coater or the like, is applied to a uniform thickness on a carrier film. Thereafter, the applied composition, usually followed by drying for 1 to 30 minutes at a temperature of 40 ~ 130 ° C., it is possible to form a resin layer. Although there is no particular limitation on the thickness of the coating film, generally, a film thickness after drying, 3 ~ 150 [mu] m, is suitably selected preferably in the range of 5 ~ 60 [mu] m.

As the carrier film, a plastic film is used, for example, can be used a polyester film such as polyethylene terephthalate (PET), polyimide films, polyamideimide films, polypropylene films, polystyrene films and the like. No particular limitation is imposed on the thickness of the carrier film, generally, it is properly selected within a range of 10 ~ 150 [mu] m. More preferably in the range of 15 ~ 130 .mu.m.

After forming the resin layer made of the curable resin composition of the present invention on a carrier film, for the purpose of preventing dust from adhering to the surface of the resin layer, further, on the surface of the resin layer, releasable cover it is preferable to laminate the film. The releasable cover film, for example, may be used polyethylene film and polytetrafluoroethylene film, polypropylene film, the surface treated paper. The cover film, when peeling off the cover film, as long as less than the adhesion between the resin layer and the carrier film.

In the present invention, the curable resin composition of the present invention on the cover film coating, to form a resin layer by drying, or may be laminated carrier film on the surface thereof. That is, the film for coating the curable resin composition of the present invention when manufacturing the dry film in the present invention, may be any of the carrier film and the cover film.

Printed circuit board of the present invention has a curable resin composition or a cured product obtained from the resin layer of the dry film of the present invention. As a method for producing a printed wiring board of the present invention, for example, the curable resin composition of the present invention, by adjusting the viscosity suitable for the coating method using the organic solvent, on a substrate, a dip coating method, flow coating, roll coating, bar coating, screen printing was applied by the method of curtain coating method or the like, causing volatile drying the organic solvent contained in the composition at a temperature of 60 ~ 100 ° C. (temporarily dried) it is, to form a resin layer of the tack-free. Also, if the dry film, after the resin layer is laminated on the substrate so as to contact with the substrate by a laminator or the like, by peeling off the carrier film to form a resin layer on the substrate.

As the base material, other printed circuit board is circuitry formed and a flexible printed circuit board in advance by copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass fabric / nonwoven epoxy, glass cloth / paper epoxy , synthetic fibers epoxy, fluorocarbon resin, polyethylene polyphenylene ether, one using the material for high-frequency circuits copper clad laminate or the like using a polyphenylene oxide-cyanate, etc., copper-clad laminate of all grades (FR-4, etc.) plate, other metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, a wafer plate.

Volatile dry performing curable resin composition of the present invention after applying the hot-air circulating drying oven, IR oven, a hot plate, in the dryer with the one having a heat source of an air heating system by convection oven or the like (steam it can be carried out using the method) blown onto the support than the method and the nozzle allowed to hot air contact countercurrent.

When the curable resin composition of the present invention is a thermosetting, for example, by thermally cured by heating to a temperature of 100 ~ 220 ° C., heat resistance, chemical resistance, moisture resistance, adhesion, electrical properties it is possible to form the characteristics excellent cured film etc. (cured product).

When the curable resin composition of the present invention is a light rigid after forming a resin layer on a printed wiring board, selectively exposing an active energy ray through a photomask having a predetermined pattern formed, dilute the unexposed portion aqueous alkali (e.g., 0.3 to 3% by weight aqueous solution of sodium carbonate) to form a pattern of a cured product was developed by. Furthermore, radiation heat cured active energy ray curable material (e.g., 100 ~ 220 ° C.), or irradiating the heat curing after active energy ray, or by finishing cure (curing) in heat curing alone, adhesion gender, to form a good cured film properties such as hardness.
Incidentally, the curable resin composition of the present invention, if it contains photobase generator, it is preferable to heat before after exposure and development, the heating condition before exposure after development, for example, 1 ~ at 60 ~ 0.99 ° C. it is preferable to heat for 60 minutes.

As an exposure apparatus used in the active energy ray irradiation, a high pressure mercury lamp, ultra-high pressure mercury lamp, a metal halide lamp, equipped with a mercury short arc lamp or the like may be a device for irradiating the ultraviolet rays in the range of 350 ~ 450 nm, Furthermore, direct imaging system (e.g., a laser direct imaging apparatus draws an image in direct laser by the CAD data from a computer) may also be used. The lamp light source or laser light source straight 描機 may be those maximum wavelength in the range of 350 ~ 450 nm. Exposure for image formation depends thickness, etc. but is generally 10 ~ 1000mJ / cm 2, preferably be in the range of 20 ~ 800mJ / cm 2.

As the developing method may be by dipping method, a shower method, a spray method, a brush method, etc., as the developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, an aqueous alkali solution such as an amine can be used.

The curable resin composition of the present invention is suitably used for forming a cured film on a printed wiring board, more preferably, is used to form a permanent coating, more preferably, a solder resist, an interlayer insulating layer, is used to form the coverlay. Further, according to the curable resin composition of the present invention, crack resistance and since it is possible to obtain an excellent cured product insulation reliability, a printed wiring board having a wiring pattern of fine-pitch high reliability is required, for example the package substrate can be suitably used especially formation of a permanent coating (especially a solder resist) for FC-BGA.

Hereinafter, the present invention will be described in more detail with reference to Examples, the present invention is not limited to the following examples. Incidentally, "parts" and "%" in the following, in particular all weight unless otherwise specified.

[Synthesis of carboxyl group-containing resin A-1]
Thermometer, autoclave equipped with a nitrogen introducing device and alkylene oxide introducing device and stirrer, novolac cresol resin (manufactured by Showa Denko KK Shonol CRG95, OH equivalent: 119.4) 119.4 parts of potassium hydroxide 1. 19 parts and introducing toluene 119.4 parts, stirring the inside of the system was replaced with nitrogen while, and Atsushi Nobori. Then gradually added dropwise 63.8 parts of propylene oxide, 125 ~ 132 ° C., it was 0 ~ 4.8kg / cm 2 at 16 hours of reaction. After cooling to room temperature, potassium hydroxide was neutralized by adding and mixing 89% 1.56 parts of phosphoric acid to the reaction solution, a non-volatile content 62.1%, hydroxyl value 182.2mgKOH / g (307. 9 g / eq.) of propylene oxide reaction solution of a novolac type cresol resin was obtained a. This was the phenolic hydroxyl group per equivalent of propylene oxide has an average 1.08 moles added.
Propylene oxide reaction solution 293.0 parts of the resulting novolak type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 252.9 parts of methyl hydroquinone 0.18 parts of toluene, a stirrer, a temperature meter and then introduced into a reactor equipped with an air blowing tube, blowing air at 10 ml / min, while stirring, was allowed to react for 12 hours at 110 ° C.. Reaction water produced by the as an azeotrope with toluene, 12.6 parts of water was distilled. After cooling to room temperature, the resulting reaction solution was neutralized with 35.35 parts of 15% sodium hydroxide solution, then washed with water. Thereafter, toluene was distilled off while replacing with diethylene glycol monoethyl ether acetate 118.1 parts by an evaporator to obtain a novolak acrylate resin solution. Next, 1.22 parts of the resulting novolac acrylate resin solution 332.5 parts of triphenylphosphine, stirrer, were introduced into a reactor equipped with a thermometer and air blowing tube, the air of 10 ml / min rate blown in, with stirring, gradually added tetrahydrophthalic anhydride 60.8 parts, was reacted for 6 hours at 95 ~ 101 ° C., cooled, and taken out. In this way, solid content of 65% to obtain a photosensitive solution of a carboxyl group-containing resin A-1 having an acid value of 87.7mgKOH / g of solids. Hereinafter referred to solution of the carboxyl group-containing photosensitive resin and the resin solution A-1.

[Synthesis of carboxyl group-containing resin A-2]
A cooling tube, equipped with a stirrer flask, A456 parts of bisphenol, 228 parts of water, were charged 649 parts of 37% formalin, maintaining the temperature of 40 ° C. or less, were added 228 parts of 25% sodium hydroxide solution, after completion of the addition 50 and reacted for 10 hours at ℃. After completion of the reaction 40 ° C. was cooled and neutralized to pH4 with 37.5% phosphoric acid solution while maintaining the 40 ° C. or less. Then to separate the stand and the aqueous layer. After addition of 300 parts of methyl isobutyl ketone was separated and uniformly dissolved, and washed 3 times with distilled water 500 parts, under reduced pressure at a temperature of 50 ° C. or less, to remove water, a solvent or the like. The resulting polymethylol compound was dissolved in 550 parts of methanol to obtain a methanol solution 1230 parts of polymethylol compound.
Some of the methanol solution of the resulting polymethylol compound was dried at room temperature in a vacuum dryer to a solid content was 55.2%.
A cooling tube, a flask equipped with a stirrer, methanol solution 500 parts of the resulting polymethylol compound, were charged 440 parts of 2,6-xylenol were homogeneously dissolved at 50 ° C.. Was removed under reduced pressure methanol 50 ° C. temperature below were uniformly dissolved. Thereafter 8 parts of oxalic acid was added and reacted at 100 ° C. 10 hours. After completion of the reaction 180 ° C., to remove distillate fraction under a reduced pressure of 50 mmHg, the novolak resin A was obtained 550 parts.
Thermometer, autoclave equipped with a nitrogen introducing device and alkylene oxide introducing device and stirrer, 130 parts of the novolak resin A, 50% aqueous sodium 2.6 parts hydroxide, toluene / methyl isobutyl ketone (weight ratio = 2/1) 100 parts, stirring the inside of the system was replaced with nitrogen while, then heated heated, 0.99 ° C., it was gradually introduced reacting 60 parts of propylene oxide at 8 kg / cm 2. The reaction was continued for about 4 hours until a gauge pressure 0.0 kg / cm 2, then cooled to room temperature. The 36% aqueous hydrochloric acid 3.3 parts to the reaction solution was added and mixed to neutralize the sodium hydroxide. The neutralized reaction product was diluted with toluene, washed three times with water, and the solvent was removed with an evaporator, a hydroxyl value of 189 g / eq. To obtain a propylene oxide adduct of novolac resin A is. This was the phenolic hydroxyl group per equivalent of propylene oxide is an average of 1 mol adduct.
Propylene oxide adduct 189 parts of thus obtained novolak resin A, 36 parts of acrylic acid, p-3.0 parts of toluene sulfonic acid, 0.1 parts of hydroquinone monomethyl ether, stirrer 140 parts of toluene, a thermometer, an air blowing tube was charged into a reactor equipped, with stirring while blowing air, the temperature was raised to 115 ° C., while the water produced by the reaction was distilled off as a toluene azeotrope, mixture was allowed to further react for 4 hours, to room temperature It cooled. The resulting reaction solution was washed with aqueous 5% NaCl solution and after removing the toluene under reduced pressure distillation, by adding diethylene glycol monoethyl ether acetate, to give a solid content of 67% of acrylate resin solution.
Next, a four-neck flask equipped with a stirrer and a reflux condenser, was charged acrylate resin solution 322 parts obtained, 0.1 part of hydroquinone monomethyl ether, 0.3 parts of triphenylphosphine, the mixture 110 ° C. It was heated to, adding tetrahydrophthalic 60 parts of phthalic anhydride, and reacted for 4 hours, cooled, and taken out. Thus photosensitive carboxyl resin solution obtained had a solids content of 70% and a solids acid value of 81mgKOH / g. Hereinafter referred to solution of the carboxyl group-containing photosensitive resin and the resin solution A-2.

[Synthesis of carboxyl group-containing resin A-3]
Diethylene glycol monoethyl ether acetate 600g ortho-cresol novolak type epoxy resin (DIC Corp. EPICLON N-695, softening point 95 ° C., epoxy equivalent weight 214, average functionality 7.6) 1070 g (glycidyl groups (aromatic rings total): 5. 0 mol), 360 g of acrylic acid (5.0 moles), and were charged hydroquinone 1.5g, was heated and stirred to 100 ° C., and uniformly dissolved.
Then, charged triphenylphosphine 4.3 g, after 2 hours the reaction was heated to 110 ° C., was further 12 hours the temperature was raised to 120 ° C.. To the resulting reaction solution, an aromatic hydrocarbon (Solvesso 0.99) 415 g, were charged tetrahydrophthalic anhydride 456.0 g (3.0 mol), the reaction for 4 hours at 110 ° C., cooled, photosensitive carboxyl to obtain a group containing resin solution. Thus the solid content of the resulting resin solution is 65%, the acid value of the solid of 89 mgKOH / g. Hereinafter referred to solution of the carboxyl group-containing photosensitive resin and the resin solution A-3.

[Synthesis of carboxyl group-containing resin A-4]
A thermometer, a stirrer, a flask equipped with a dropping funnel, and a reflux condenser, 325.0 parts of dipropylene glycol monomethyl ether was heated to 110 ° C. as a solvent, 174.0 parts of methacrylic acid, .epsilon.-caprolactone-modified methacrylate (average molecular weight 314) 174.0 parts, 77.0 parts of methyl methacrylate, 222.0 parts of dipropylene glycol monomethyl ether, and a polymerization catalyst as t- butyl peroxy-2-ethylhexanoate (manufactured by NOF CORPORATION Perbutyl O ) a mixture of 12.0 parts, was added dropwise over 3 hours, and further stirred for 3 hours at 110 ° C., the polymerization catalyst is deactivated to obtain a resin solution.
After cooling the resin solution, 289.0 parts of Daicel Chemical Industries, Ltd. Cyclomer A200, 3.0 parts of triphenylphosphine, hydroquinone monomethyl ether 1.3 parts was added, the temperature was raised to 100 ° C., by stirring perform ring-opening addition reaction of an epoxy group to obtain a photosensitive carboxyl resin solution.
Resin solution obtained in this way, a weight average molecular weight (Mw) of 15,000, and a solid content of 57%, an acid value of solids was 79.8mgKOH / g. Hereinafter referred to solution of the carboxyl group-containing photosensitive resin and the resin solution A-4.

[Synthesis of epoxy resin B-1 having a silsesquioxane skeleton]
90.0 parts of γ- glycidoxypropyltrimethoxysilane, were charged to a reaction vessel 93 parts of methyl isobutyl ketone was heated to 80 ° C.. After heating, it was continuously added dropwise over a 21.6 parts 0.1 wt% potassium hydroxide aqueous solution for 30 minutes. After the addition, the mixture was allowed to react for 5 hours at 80 ° C. while removing formed methanol. After completion of the reaction, the washing liquid was repeatedly washed with water until neutral. Then give the 69 parts of an epoxy resin having a silsesquioxane skeleton by removing the solvent under reduced pressure. The epoxy equivalent of the resulting epoxy resin is 165 g / eq. The weight average molecular weight was 2000.

[Synthesis of epoxy resin B-2 having a silsesquioxane skeleton]
90.0 parts of γ- glycidoxypropyltrimethoxysilane, 3.0 parts of phenyltrimethoxysilane, 2.0 parts of methyl trimethoxysilane were charged into a reaction vessel 93 parts of methyl isobutyl ketone was heated to 80 ° C.. After heating, it was continuously added dropwise over a 21.6 parts 0.1 wt% potassium hydroxide aqueous solution for 30 minutes. After the addition, the mixture was allowed to react for 5 hours at 80 ° C. while removing formed methanol. After completion of the reaction, the washing liquid was repeatedly washed with water until neutral. Then give the 69 parts of an epoxy resin having a silsesquioxane skeleton by removing the solvent under reduced pressure. The epoxy equivalent of the resulting epoxy resin is 176 g / eq. The weight average molecular weight was 2200.

[Synthesis of epoxy resin B-3 having a silsesquioxane skeleton]
65.0 parts of γ- glycidoxypropyltrimethoxysilane, 12.0 parts of phenyl trimethoxy silane, 8.0 parts of methyl trimethoxysilane were charged into a reaction vessel 93 parts of methyl isobutyl ketone was heated to 80 ° C.. After heating, it was continuously added dropwise over a 21.6 parts 0.1 wt% potassium hydroxide aqueous solution for 30 minutes. After the addition, the mixture was allowed to react for 5 hours at 80 ° C. while removing formed methanol. After completion of the reaction, the washing liquid was repeatedly washed with water until neutral. Then give the 69 parts of an epoxy resin having a silsesquioxane skeleton by removing the solvent under reduced pressure. The epoxy equivalent of the resulting epoxy resin is 236 g / eq. The weight average molecular weight was 2200.

[Synthesis of epoxy resin B-4 having a silsesquioxane skeleton]
40.0 parts of γ- glycidoxypropyltrimethoxysilane, 25.0 parts of phenyl trimethoxy silane, 15.0 parts of methyltrimethoxysilane, were charged to the reaction vessel 93 parts of methyl isobutyl ketone was heated to 80 ° C.. After heating, it was continuously added dropwise over a 21.6 parts 0.1 wt% potassium hydroxide aqueous solution for 30 minutes. After the addition, the mixture was allowed to react for 5 hours at 80 ° C. while removing formed methanol. After completion of the reaction, the washing liquid was repeatedly washed with water until neutral. Then give the 69 parts of an epoxy resin having a silsesquioxane skeleton by removing the solvent under reduced pressure. The epoxy equivalent of the resulting epoxy resin is 400 g / eq. The weight average molecular weight was 2200.

Surface-treated inorganic filler (silica) Adjustment of C-1]
And spherical silica (Denka Co. SFP-20M) 70 g, and PMA (propylene glycol monomethyl ether acetate) 28 g as a solvent, a silane coupling agent (manufactured by Shin KBM-503) with a 2g are uniformly dispersed, silica solvents to obtain a dispersion product D-1.

[Surface treated inorganic filler adjustment (barium sulfate) C-2]
And 70g of barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd. B-30 (alumina surface treated barium sulfate)), and 28g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and a and dispersing agent (BYK Co. BYK-111) 2 g was uniformly dispersed to obtain a barium sulfate solvent dispersion products D-2.

[Adjustment of silica which is not surface-treated]
The resulting spherical silica (Denka Co. SFP-20M) 70 g, and PMA (propylene glycol monomethyl ether acetate) 28 g as a solvent, and dispersing agent (BYK Co. BYK-111) and 2g and are uniformly dispersed, silica solvent dispersion products of It was.

[Examples 1-16, Comparative Examples 1-5]
The above resin solution (varnish), with various components shown in Table 1 were blended at proportions shown in Table 1 (parts by mass), it was preliminarily mixed using a stirrer and kneaded with a three-roll mill, a curable resin composition things were prepared.

<Glass transition temperature Tg and the coefficient of thermal expansion CTE>
(Examples 1-15, Comparative Examples 1-5)
On the copper foil substrate it was entirely coated with a curable resin composition to a dry film thickness of about 40μm by screen printing. This was dried at 80 ° C., by cooling to room temperature, to form a resin layer made of the curable resin composition to obtain an evaluation substrate with an uncured sample of each Example and Comparative Example. In contrast, ORC Co. HMW680GW (metal halide lamp, scattered light) by the optimal exposure amount: was exposed through a strip-shaped negative mask of 50 mm × 3 mm at 800 mJ. Then, 1wt of 30 ℃. % And developed by sodium carbonate aqueous solution to obtain a pattern of the cured film. After further irradiated with ultraviolet rays to the integrated exposure amount as 1000 mJ, and cured by heating for 1 hour at 160 ° C..
The cured film of the evaluation substrate obtained by the peeling of a copper foil was evaluated. Measurement, TMA measurement device (manufactured by Shimadzu Corporation, model name: TMA6000) performed using, Tg and CTEα1 (0 ℃ -50 ℃), were evaluated with CTEα2 (200 ℃ -250 ℃). The evaluation criteria are as follows.
(Example 16)
On the copper foil substrate it was entirely coated with a curable resin composition to a dry film thickness of about 40μm by screen printing. This was dried at 80 ° C., by cooling to room temperature, to form a resin layer made of the curable resin composition. To obtain an evaluation substrate having a cured film which was cured by heating 1 hour at 160 ° C..
The cured film of the evaluation substrate obtained by the peeling of a copper foil was evaluated by cutting the 50 mm × 3 mm strip. Measurement, TMA measurement device (manufactured by Shimadzu Corporation, model name: TMA6000) performed using, Tg and CTEα1 (0 ℃ -50 ℃), were evaluated with CTEα2 (200 ℃ -250 ℃). The evaluation criteria are as follows.
(Tg)
◎ ... 150 ℃ or more ○ ... 145 ℃ more than 150 ℃ △ ... 140 ℃ more than 145 ℃ less than × ... 140 less than ℃ (CTEα1)
◎ ... less than 40ppm ○ ... 40ppm more than 50ppm less than △ ... 50ppm more than 60ppm less than × ... 60ppm or higher (CTEα2)
◎ ... less than 110ppm ○ ... or more and less than 110ppm 120ppm △ ... 120ppm more than 130ppm less than × ... 130ppm or more

<Elastic modulus E and Tanδ>
(Examples 1-15, Comparative Examples 1-5)
On the copper foil substrate it was entirely coated with a curable resin composition to a dry film thickness of about 40μm by screen printing. This was dried at 80 ° C., by cooling to room temperature, to form a resin layer made of the curable resin composition to obtain an evaluation substrate with an uncured sample of each Example and Comparative Example. In contrast, ORC Co. HMW680GW (metal halide lamp, scattered light) by was exposed through a negative mask strip of 50 mm × 5 mm at 800 mJ. Then, 1wt of 30 ℃. % And developed by sodium carbonate aqueous solution to obtain a pattern of cured film. After further irradiated with ultraviolet rays to the integrated exposure amount as 1000 mJ, to obtain an evaluation substrate having a 1 hour heat curing to cured films at 160 ° C..
The cured coating of the evaluation substrate obtained by the peeling of a copper foil was evaluated. Measurement, DMA measurement device (manufactured by Shimadzu Corporation model name: DMS6100) performed using, we were evaluated E at 260 ℃. The tan [delta, Hitachi Hi-Tech Co., Ltd. DMS6100 by heating 5 ° C. to 300 ° C. from 25 ° C. / min, measured at a frequency 1 Hz, pull sine wave mode, it took the maximum value in the temperature measurement region.
(Example 16)
On the copper foil substrate it was entirely coated with a curable resin composition to a dry film thickness of about 40μm by screen printing. To obtain an evaluation substrate having a cured film which was heated for 1 hour curing at 160 ° C..
The cured coating of the evaluation substrate obtained by the peeling of a copper foil was evaluated. Measurement, DMA measurement device (manufactured by Shimadzu Corporation model name: DMS6100) performed using, we were evaluated E at 260 ℃. The tan [delta, Hitachi Hi-Tech Co., Ltd. DMS6100 by heating 5 ° C. to 300 ° C. from 25 ° C. / min, measured at a frequency 1 Hz, pull sine wave mode, it took the maximum value in the temperature measurement region.
The evaluation criteria are as follows.
(Modulus of elasticity E)
◎ ... 1 × 10 9 Pa or more ○ ... 5 × 10 8 1 × less than 10 9 Pa or more Pa △ ... 1 × 10 8 Pa more than 5 × 10 8 × ... 1 × less than 10 8 Pa less than Pa (Tanδ)
◎ ... 0.20 less than ○ ... 0.20 or more and 0.25 or less than △ ... 0.25 0.30 less than × ... 0.30 or higher

<Warp>
(Examples 1-15, Comparative Examples 1-5)
The CZ treated 35μm copper foil substrate was entirely coated with a curable resin composition to a dry film thickness of 20μm by screen printing. This was dried at 80 ° C., by cooling to room temperature, to form a resin layer made of the curable resin composition to obtain an evaluation substrate with an uncured sample of each Example and Comparative Example. In contrast, ORC Co. HMW680GW (metal halide lamp, scattered light) by the optimal exposure amount was performed on the entire surface exposure at 800 mJ. Then, 1wt of 30 ℃. % Followed by development with an aqueous sodium carbonate solution, to obtain a pattern of the cured film. After further irradiated with ultraviolet rays to the integrated exposure amount as 1000 mJ, and cured by heating for 1 hour at 160 ° C..
Cut a cured film of the evaluation substrate obtained by above 50 mm × 50 mm, and the cured film surface and allowed to stand on a horizontal base downwards. After standing, it was evaluated as a horizontal table for four corners by measuring the distance to the Cu foil, respectively an average value of the following cured film cut.
(Example 16)
The CZ treated 35μm copper foil substrate was entirely coated with a curable resin composition to a dry film thickness of 20μm by screen printing. This was dried at 80 ° C., by cooling to room temperature, to form a resin layer made of the curable resin composition. This was cured by heating 1 hour at 160 ° C., to obtain an evaluation substrate having a cured film.
Cut a cured film of the evaluation substrate obtained by above 50 mm × 50 mm, and the cured film surface and allowed to stand on a horizontal base downwards. After standing, it was evaluated as a horizontal table for four corners by measuring the distance to the Cu foil, respectively an average value of the following cured film cut.
◎ ... less than 10mm ○ ... less than 15mm more than 10mm △ ... 15mm more than 20mm less than × ... 20mm or more

<Reaction rate>
(Examples 1-15, Comparative Examples 1-5)
Plated copper substrate treated with the etching rate 1 [mu] m / m 2 at CZ8101, was entirely coated to a dry film thickness of about 20μm by screen printing a curable resin composition to the surface. This was dried at 80 ° C., by cooling to room temperature, to form a resin layer made of the curable resin composition to obtain an evaluation substrate alpha. In contrast, ORC Co. HMW680GW (metal halide lamp, scattered light) by the optimal exposure amount was performed on the entire surface exposure at 800 mJ. Then, 1wt of 30 ℃. % And treated with aqueous sodium carbonate solution to obtain a cured film. After further irradiated with ultraviolet rays to the integrated exposure amount as 1000 mJ, and cured by heating under the following conditions, to obtain an evaluation substrate beta.
Evaluation board α obtained by the above, performed FT-IR measurement of the beta, it was measured reaction rate of the epoxy groups.
The reaction of the epoxy groups, using Microscope Spotlight200 as measuring device was calculated from the peak height of around 913cm -1 is vibration from epoxy groups.
(Example 16)
Plated copper substrate treated with the etching rate 1 [mu] m / m 2 at CZ8101, was entirely coated to a dry film thickness of about 20μm by screen printing a curable resin composition to the surface. This was dried at 80 ° C., by cooling to room temperature, to form a resin layer made of the curable resin composition to obtain an evaluation substrate alpha. This heated to cure to obtain an evaluation substrate β under the following conditions.
Evaluation board α obtained by the above, performed FT-IR measurement of the beta, it was measured reaction rate of the epoxy groups.
The reaction of the epoxy groups, using Microscope Spotlight200 as measuring device was calculated from the peak height of around 913cm -1 is vibration from epoxy groups.
◎ ... 0.99 ° C. 60min epoxy reaction rate of 98% or more by curing achieved ○ ... 160 ° C. 60min achieved epoxy reaction rate of 98% or more by curing △ ... 170 ° C. 60min epoxy reaction rate of 98% or more at curing achieved × ... 170 ° C. 60min the reaction rate of less than 98% epoxy by curing

<Evaluation of Resolution>
(Examples 1-15, Comparative Examples 1-5)
Plated copper substrate treated with the etching rate 1 [mu] m / m 2 at CZ8101, was entirely coated to a dry film thickness of about 20μm by screen printing a curable resin composition to the surface. This was dried at 80 ° C., by cooling to room temperature, to form a resin layer made of the curable resin composition. In contrast, ORC Co. HMW680GW (metal halide lamp, scattered light) by the optimal exposure amount: pattern exposure was performed at 800 mJ. Then, 1wt of 30 ℃. % And developed by sodium carbonate aqueous solution to obtain a pattern of the cured film. After further irradiated with ultraviolet rays to the integrated exposure amount as 1000 mJ, and cured by heating for 1 hour at 160 ° C..
To observe the opening diameter of the evaluation substrate obtained by the above-mentioned, halation, a check to see that there is no occurrence of the undercut was evaluated.
◎ ... not obtained satisfactory opening diameter at good opening diameter × ... 100 [mu] m in good opening diameter △ ... 100 [mu] m in good opening diameter ○ ... 70 [mu] m at 50 [mu] m, or development Not

<Insulation reliability (HAST resistance)>
(Examples 1-15, Comparative Examples 1-5)
L / S = 20/20 using a substrate comb pattern is formed, and the entire surface coated with a curable resin composition to a dry film thickness of about 20μm by screen printing. This was dried at 80 ° C., by cooling to room temperature, to form a resin layer made of the curable resin composition to obtain an evaluation substrate with an uncured sample of each Example and Comparative Example. In contrast, ORC Co. HMW680GW (metal halide lamp, scattered light) by the optimal exposure amount was performed on the entire surface exposure at 800 mJ. Then, 1wt of 30 ℃. % And developed by sodium carbonate aqueous solution to obtain a pattern of the cured film. After further irradiated with ultraviolet rays to the integrated exposure amount as 1000 mJ, and cured by heating for 1 hour at 160 ° C..
Thereafter obtained evaluation substrate connecting electrode 130 ° C., placed in a high temperature and high humidity bath under an atmosphere of 85% humidity, carried out HAST test under the conditions of the voltage 5V, electrical insulation falls below 1 × 10 6 Ω the time was measured at the time was.
(Example 16)
L / S = 20/20 using a substrate comb pattern is formed, and the entire surface coated with a curable resin composition to a dry film thickness of about 20μm by screen printing. This was dried at 80 ° C., by cooling to room temperature, to form a resin layer made of the curable resin composition. This was cured by heating 1 hour at 160 ° C., to obtain an evaluation substrate having a cured film.
Thereafter obtained evaluation substrate connecting electrode 130 ° C., placed in a high temperature and high humidity bath under an atmosphere of 85% humidity, carried out HAST test under the conditions of the voltage 5V, electrical insulation falls below 1 × 10 6 Ω the time was measured at the time was.
◎ ... 300h pass
○ ... 200h pass
△ ... 150h pass
× ... NG within at 150h

<Crack resistance (TCT resistance)>
(Examples 1-15, Comparative Examples 1-5)
Pad pitch on the evaluation board for FC-BGA formed with 250μm pitch and entirely coated with a curable resin composition. It was dried, by cooling to room temperature, to form a resin layer made of the curable resin composition. In contrast, the optimum exposure amount: at 800 mJ, was direct imaging exposure on a copper pad in the aperture size of the SRO (Solder Resist Opening) 80μm. Thereafter, development by injecting 1 wt% aqueous solution of sodium carbonate 30 ° C., to obtain a pattern of the cured film. After further irradiated with ultraviolet rays to the integrated exposure amount as 1000 mJ, and cured by heating for 1 hour at 160 ° C.. Thereafter, Au plating, solder bump formation, mounted Si chips, to obtain an evaluation substrate.
The evaluation substrate obtained by the above was placed in a thermal cycle machine temperature cycle is performed at between -65 ° C. and 0.99 ° C., was TCT (Thermal Cycle Test). Then, when 600 cycles were observed surface of the cured film during 800 cycles and at 1000 cycles. The evaluation criteria were as follows.
(Example 16)
Pad pitch on the evaluation board for FC-BGA formed with 250μm pitch and entirely coated with a curable resin composition. It was dried, by cooling to room temperature, to form a resin layer made of the curable resin composition. This was cured by heating 1 hour at 160 ° C., to obtain a substrate having a cured film. In contrast top diameter at a CO 2 laser processing machine (manufactured by Hitachi Via Mechanics, Ltd.) was formed via the cured film such that the 80 [mu] m. Thereafter, Au plating, solder bump formation, mounted Si chips, to obtain an evaluation substrate.
The evaluation substrate obtained by the above was placed in a thermal cycle machine temperature cycle is performed at between -65 ° C. and 0.99 ° C., was TCT (Thermal Cycle Test). Then, when 600 cycles were observed surface of the cured film during 800 cycles and at 1000 cycles. The evaluation criteria were as follows.
◎ ... 1000 no abnormality in the cycle ○ ... no abnormalities at 800 cycles, no abnormality in cracking △ ... 600 cycle in the 1000 cycle, cracking in cracking × ... 600 cycles at 800 cycles

Figure JPOXMLDOC01-appb-T000010

Figure JPOXMLDOC01-appb-T000011

Figure JPOXMLDOC01-appb-T000012
* 1: carboxyl groups synthesized above-containing resin solution A-1
* 2: carboxyl groups synthesized above-containing resin solution A-2
* 3: carboxyl group-containing resin solution A-3 synthesized in the above
* 4: carboxyl group-containing resin solution A-4 synthesized in the above
* 5: BASF Japan Co. Irgacure TPO (2,4,6-trimethyl benzoyl - diphenyl - phosphine oxide)
* 6: BASF Japan Co. Irgacure 907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one)
* 7: BASF Japan Co. Irgacure OXE02 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- carbazol-3-yl]-1-(o-acetyl oxime)
* 8: epoxy resin B-1 having the synthesized silsesquioxane skeleton in the
* 9: Epoxy resin B-2 having the synthesized silsesquioxane skeleton in the
* 10: epoxy resin B-3 having a synthesized silsesquioxane skeleton in the
* 11: epoxy resin B-4 having the synthesized silsesquioxane skeleton in the
* 12: manufactured by Mitsubishi Chemical Corporation jER828 (bisphenol A type epoxy resin)
* 13: The Dow Chemical Co., Ltd. DEN431 (a phenol novolac epoxy resin)
* 14: DIC Corporation N-870 75EA (bisphenol A novolac type epoxy resin)
* 15: DIC Corporation EXA-724 (triphenyl methane type epoxy resin))
* 16: Adjust surface treated silica solvent dispersion products C-1 above (... Homogeneously dispersed spherical silica PMA methacrylic surface treated silica content 70 wt% (solids) silica having an average particle diameter of 0.8 [mu] m)
* 17:... Homogeneously dispersed the barium sulfate surface-treated was adjusted with a solvent dispersion products C-2 (the barium sulfate in the PMA alumina surface treated barium sulfate content 70 wt% (solids) of barium sulfate-average particle diameter (0 .5μm))
* 18: the adjustment surface untreated silica solvent dispersion products (... Homogeneously dispersed spherical silica PMA surface treatment free silica content 70 wt% (solids) silica having an average particle diameter of 0.8 [mu] m)
* 19: that the precipitated barium sulphate was homogeneously dispersed in PMA. Barium sulfate content of 70 wt% (solids). Not a surface treatment.
* 20: manufactured by Nippon Kayaku Co., Ltd. DPHA (dipentaerythritol hexaacrylate)
* 21: blue colorant, a colorant content of 12 wt%
* 22: Yellow colorant, a colorant content of 10 wt%
* 23: DICY (dicyandiamide)
* 24: Not rated

From the results shown in the above table, the cured product of the curable resin compositions of Examples 1 to 16 of the present invention, it can be seen that excellent crack resistance and insulation reliability. In contrast, the use of curable resin compositions of Comparative Examples 1-5, it particularly elastic modulus at high temperature (E) low, it is difficult to obtain a high degree of crack resistance and insulation reliability.

Claims (8)

  1. (A) a carboxyl group-containing resin, an epoxy resin having a (B) silsesquioxane skeleton,
    Curable resin composition characterized by containing a.
  2. Further (C) The curable resin composition according to claim 1, characterized in that it contains the surface treated inorganic filler.
  3. Wherein (A) a carboxyl group-containing resin, the curable resin composition according to claim 1, characterized by having a structure represented by the following general formula (1).
    Figure JPOXMLDOC01-appb-I000001

    (Wherein, R 1 ~ R 4 represents a hydrogen atom or an alkyl group independently, k represents any value of 0.3 to 10.)
  4. Wherein (A) a carboxyl group-containing resin, the curable resin composition according to claim 1, characterized by having a structure represented by the following general formula (2).
    Figure JPOXMLDOC01-appb-I000002

    (Wherein, R 5 ~ R 7 each independently represent a hydrogen atom or an alkyl group, Z is represents an acid anhydride residue, m represents any value of 0.3 to 10.)
  5. The epoxy resin (B) having a silsesquioxane skeleton, a curable resin composition according to claim 1, characterized by having a structure represented by the following general formula (3).
    Figure JPOXMLDOC01-appb-I000003

    (Wherein, R 8 ~ R 11 are each independently a group or an organic group having an SiO bond, at least one of R 8 ~ R 11 is a group having an epoxy group.)
  6. Coated claim 1 curable resin composition according to the film, the dry film characterized by having a resin layer obtained by drying.
  7. The curable resin composition according to any one of claims 1 to 5, or a cured product which is characterized by being obtained by curing the resin layer of the dry film according to claim 6, wherein.
  8. Printed wiring board characterized by having a claim 7 the cured product according.
PCT/JP2017/013454 2016-03-31 2017-03-30 Curable resin composition, dry film, cured product and printed wiring board WO2017170959A1 (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000281790A (en) * 1999-03-30 2000-10-10 Nippon Steel Chem Co Ltd Silicon resin and photosensitive resin composition containing same
JP2009126901A (en) * 2007-11-21 2009-06-11 Nof Corp Thermosetting resin composition for sealing optical semiconductor
JP2010106205A (en) * 2008-10-31 2010-05-13 Nof Corp Thermosetting resin composition
WO2011155613A1 (en) * 2010-06-11 2011-12-15 日本化薬株式会社 Curable resin composition and substance obtained by curing same
JP2013541733A (en) * 2010-09-30 2013-11-14 コーロン インダストリーズ インク The organic insulating film for a photosensitive resin composition
JP2014081611A (en) * 2012-09-28 2014-05-08 Taiyo Ink Mfg Ltd Photocurable resin composition, print circuit board, and production method of photocurable composition
JP2015227441A (en) * 2014-05-09 2015-12-17 太陽インキ製造株式会社 Curable resin composition, dry film, and printed wiring board
JP2016160420A (en) * 2015-03-05 2016-09-05 Jnc株式会社 Thermosetting composition, cured film, substrate with cured film, electronic component, and display device

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000281790A (en) * 1999-03-30 2000-10-10 Nippon Steel Chem Co Ltd Silicon resin and photosensitive resin composition containing same
JP2009126901A (en) * 2007-11-21 2009-06-11 Nof Corp Thermosetting resin composition for sealing optical semiconductor
JP2010106205A (en) * 2008-10-31 2010-05-13 Nof Corp Thermosetting resin composition
WO2011155613A1 (en) * 2010-06-11 2011-12-15 日本化薬株式会社 Curable resin composition and substance obtained by curing same
JP2013541733A (en) * 2010-09-30 2013-11-14 コーロン インダストリーズ インク The organic insulating film for a photosensitive resin composition
JP2014081611A (en) * 2012-09-28 2014-05-08 Taiyo Ink Mfg Ltd Photocurable resin composition, print circuit board, and production method of photocurable composition
JP2015227441A (en) * 2014-05-09 2015-12-17 太陽インキ製造株式会社 Curable resin composition, dry film, and printed wiring board
JP2016160420A (en) * 2015-03-05 2016-09-05 Jnc株式会社 Thermosetting composition, cured film, substrate with cured film, electronic component, and display device

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