TW202035468A - Curable composition, dry film, cured product, and electronic component - Google Patents

Abstract

Provided are a curable composition, a dry film, a cured product, and an electronic component, said curable composition including an alkali-soluble resin (A), a photopolymerization initiator (B), an epoxy resin (C), a silicon compound (D), a hydrophilic silica (E), and an organic thixotropic agent (F). The curable composition contains hydrophilic silica and a silicon-based surface conditioner but also has good soldering properties and resolves the issues of silica flocculation and precipitation. As a result, the issues of flocculation and precipitation of hydrophilic silica inside a curable composition are resolved and, when the curable composition is coated upon a base material, the silicon compound (D) maintains base material wettability and, at the same time, improves flux wettability for the obtained cured product, thereby providing improved soldering properties when the cured product is used as a solder resist.

Description

Curable composition, dry film, cured product and electronic parts

The present invention relates to a curable composition, a dry film, a hardened product, and electronic parts, and particularly relates to an alkali-developable hardenable composition, the dry film, the hardened product, and the electronic component with the hardened product.

In the past, solder resists for printed circuit boards for civilian use or printed wiring boards for industrial use, based on the viewpoint of high precision and high density, were used after ultraviolet radiation to form images by development, and heat and/or light In the liquid development type solder resist that is work-hardened by irradiation (formally hardened), among the liquid development type solder resists, based on environmental concerns, the mainstream is the alkaline development type photoprotective that uses an aqueous alkaline solution as the developer Flux.

Generally, in the solder resist composition used to form a photo solder resist on the substrate and coated on the substrate, in order to improve the wettability of the solder resist composition to the substrate, and to improve the leveling (flatness) of the coating film, And add a silicone-based surface regulator.

After forming the light solder resist on the substrate, the parts are mounted on the substrate by soldering. However, since the wettability of the molten solder to the substrate is low, the solder resist is included in order to improve the wettability (cleaning of the soldering surface and oxidation resistance) The surface of the substrate is coated with flux.

Therefore, through the review of the present inventors, it is understood that if the solder resist formed on the substrate contains a polysiloxy-based surface modifier, the solder flux does not adhere to the substrate and the solderability is reduced.

On the other hand, it is well known that in order to strengthen the rigidity of the solder resist and suppress the hardening shrinkage of the solder resist composition, silica is added as an inorganic filler to the solder resist composition.

In Patent Document 1, as the above-mentioned prior art solder resist composition, Patent Document 1 discloses an alkali-developing type photo-curable and thermo-curable solder resist composition containing a silicone-based surface modifier as a comparative example. 2. It reveals an alkali-developing photo-curable and thermo-curable solder resist composition containing molten spherical silica without surface modification treatment as an inorganic powder. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2009-194222 A

[The problem to be solved by the invention]

According to the examples of Patent Document 1, the alkali-developing photo-curable and thermo-curable solder resist composition containing a silicone-based surface modifier improves the wettability of the solder resist composition to the substrate, but due to the formed The solder resist will prevent the flux from sticking, so it will reduce the solderability.

In addition, the alkali-developing photo-curable and thermo-curable solder resist composition according to Comparative Example 2 of Patent Document 1 is hydrophilic because the added silica is not subjected to surface modification treatment, so this occurs The problem of aggregation and precipitation, for example, the surface must be modified to be hydrophobic to eliminate the problem of aggregation and precipitation. In addition, the alkali-developing photo-curable and thermo-curable solder resist composition of Comparative Example 2 did not add a silicone-based surface modifier, so the wettability of the solder resist composition to the substrate could not be improved.

The present invention has been accomplished in view of the above-mentioned problems, and its object is to provide a curable composition and dry composition that contain hydrophilic silica and polysiloxane-based surface modifiers, have good weldability, and eliminate the problems of silica agglomeration and precipitation. Films, hardened objects and electronic parts. [Means to solve the problem]

The inventors of the present invention conducted active reviews in order to achieve the above objects. As a result, it was unexpectedly discovered that when polysiloxane compound, hydrophilic silica and organic thixotropic agent are formulated, the wettability of the copper-clad substrate and solder resist composition can be maintained, and the problem of agglomeration and precipitation of hydrophilic silica can be eliminated. And the problem caused by the non-sticking of the soldering flux of the polysiloxane compound, thus the present invention has been completed.

That is, it has been found that the above-mentioned objects of the present invention can be achieved by the following hardening composition, the characteristics of which include: (A) Alkali-soluble resin, (B) photopolymerization initiator, (C) epoxy resin, (D) Polysiloxane compound, (E) Hydrophilic silica, and (F) Organic thixotropic agent.

The curable composition of the present invention further preferably (E) the median diameter D50 of the hydrophilic silica is 0.2 μm or more and 2.0 μm or less.

In addition, the amount of (F) organic thixotropic agent is preferably 0.01 parts by mass or more and 15 parts by mass or less relative to 100 parts by mass of (E) hydrophilic silica, and relative to (D) polysiloxane compound 2 mass Parts, 0.05 parts by mass or more.

Furthermore, it is preferable to further contain (G) antioxidant.

In addition, the above-mentioned object of the present invention can be achieved by a dry film, a cured product, and electronic parts. The feature of the dry film is obtained by coating and drying the curable composition of the present invention on a carrier film. The characteristic of the cured product is obtained by coating the curable composition of the present invention on a substrate and drying the resulting dry coating and curing, or coating the aforementioned curable composition on a carrier film and drying the resulting dry film It is obtained by hardening the coating film laminated on the substrate, and The characteristic of the electronic component is to have the hardened object. [Invention Effect]

According to the present invention, the problem of agglomeration and precipitation of hydrophilic silica in the curable composition can be eliminated. When the curable composition is applied to the substrate, the (D) polysiloxane compound can maintain the resistance to the substrate. The wettability of the flux can also improve the wettability of the flux to the obtained hardened material. Therefore, when the hardened material is used as a solder resist, the weldability improvement effect can be obtained.

＜Curable composition＞

The curable composition of the present invention includes: (A) Alkali-soluble resin, (B) photopolymerization initiator, (C) epoxy resin, (D) Polysiloxane compound, (E) Hydrophilic silica, and (F) Organic thixotropic agent.

[(A) Alkali-soluble resin] Alkali-soluble resin is a resin that can dissolve the curable composition in an alkali developing solution, that is, it can be developed by alkali.

As the alkali-soluble resin, a carboxyl group-containing resin or a phenol resin is preferably used. Particularly, when a carboxyl group-containing resin is used, it is preferable in terms of developability.

As the carboxyl group-containing resin, various conventionally known carboxyl group-containing resins that have a carboxyl group in the molecule and further do not have an ethylenically unsaturated group (non-photosensitive) or have an ethylenically unsaturated group (photosensitive) can be used.

In the present invention, the so-called ethylenically unsaturated group is a substituent having an ethylenically unsaturated bond, for example, vinyl group, (meth)acrylic acid group, and from the viewpoint of reactivity, (meth)propylene is preferred.醯基. Here, the so-called (meth)acryloyl group is a general term for alloyl group and methacryloyl group.

Specific examples of the carboxyl group-containing resin that does not have an ethylenically unsaturated group include the following compounds (either oligomer or polymer).

(1) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, etc., and carboxyl-containing groups such as dimethylol propionic acid and dimethylol butyric acid Diol compounds, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, bisphenol A alkylene oxide adduct diols, phenolic hydroxyl groups and alcoholic properties Carboxyl-containing urethane resin obtained by polyaddition reaction of diol compound such as hydroxyl compound.

(2) Carboxyl-containing urethane resin obtained by polyaddition reaction of diisocyanate and carboxyl-containing diol compound.

(3) By copolymerizing unsaturated carboxylic acids such as (meth)acrylic acid and unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc. Obtained carboxyl-containing resin.

(4) React bifunctional epoxy resin or bifunctional oxetane resin with dicarboxylic acids such as adipic acid, phthalic acid and hexahydrophthalic acid to add phthalic acid to the hydroxyl group produced A carboxyl-containing polyester resin made of dibasic acid anhydrides such as formic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.

(5) The carboxyl group-containing resin is obtained by ring-opening the epoxy resin or oxetane resin and reacting the polybasic acid anhydride with the generated hydroxyl group.

(6) The reaction product and the polybasic acid anhydride of the number of polyhydric alcohols obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule, that is, a polyphenol compound and an alkylene oxide such as ethylene oxide and propylene oxide A carboxyl-containing resin obtained by the reaction.

Moreover, as a specific example of the carboxyl group-containing resin which has an ethylenically unsaturated group, the following compounds (any one of an oligomer and a polymer) are mentioned, for example. In addition, the ethylenically unsaturated bond in the carboxyl group-containing resin is preferably acrylic acid or methacrylic acid or derivatives derived from these.

(7) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and carboxyl-containing diols such as dimethylol propionic acid and dimethylol butyric acid Compounds, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, phenolic hydroxyl groups and A carboxyl group-containing photosensitive urethane resin obtained by the polyaddition reaction of a glycol compound such as an alcoholic hydroxyl compound.

(8) Combining diisocyanate with bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bixylenol epoxy resin, (Meth)acrylates of bifunctional epoxy resins such as phenolic epoxy resins or partial acid anhydride modification products, carboxyl-containing photosensitive polyurethane obtained by the polyaddition reaction of carboxyl-containing diol compounds Resin.

(9) In the synthesis of the resin of (7) or (8) above, a compound having one hydroxy group and one or more (meth)acryloyl groups in the molecule such as hydroxyalkyl (meth)acrylate is added to proceed Terminal (meth)acrylated carboxyl group-containing photosensitive urethane resin.

(10) In the resin synthesis of (8) or (9) above, a molar reactant such as isophorone diisocyanate and pentaerythritol triacrylate is added. The molecule has one isocyanate group and more than one (methyl) Acrylic compound terminal (meth)acrylated carboxyl group-containing photosensitive urethane resin.

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

(12) The hydroxyl group of the bifunctional (solid) epoxy resin is further reacted with (meth)acrylic acid with the polyfunctional epoxy resin epoxidized by epichlorohydrin, and the resulting hydroxyl group is added to the dibasic acid anhydride for the carboxyl-containing photosensitive性resin.

(13) The bifunctional oxetane resin is reacted with dicarboxylic acids such as adipic acid, phthalic acid, and hexahydrophthalic acid to add phthalic anhydride and tetrahydrophthalic acid to the primary hydroxyl group produced. Dibasic acid anhydrides such as hydrogen phthalic anhydride and hexahydrophthalic anhydride are carboxyl-containing polyester photosensitive resins.

(14) The reaction product of polyol resin and the like obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule, that is, a polyphenol compound and an alkylene oxide such as ethylene oxide and propylene oxide, and (meth)acrylic acid A carboxyl group-containing photosensitive resin obtained by reacting a monocarboxylic acid containing an unsaturated group, and the resulting reaction product reacts with a polybasic acid anhydride.

(15) The reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate and propylene carbonate and an unsaturated group-containing monocarboxylic acid is obtained by reacting A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

(16) A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth)acrylic groups in one molecule to the resins of (7) to (15) above.

These photosensitive carboxyl group-containing resins may also be used as those other than those described in (7) to (16), and may be used alone or in combination of plural kinds. Particularly, among carboxyl group-containing resins, a resin having an aromatic ring is preferable.

Regardless of whether the above-mentioned carboxyl group-containing resin is photosensitive or non-photosensitive, the following can be said. That is, since there are many carboxyl groups in the main chain and the side chain of the polymer, it can be developed by dilute alkali aqueous solution.

The acid value of the carboxyl group-containing resin is preferably in the range of 40 to 200 mgKOH/g, more preferably in the range of 45 to 120 mgKOH/g. When the acid value of the carboxyl group-containing resin is within this range, the alkali development becomes easier, and the dissolution of the developer solution to the exposed area can be suppressed, the line will not be too thin, and the developer will not dissolve and peel off. Graphic type.

In addition, the weight average molecular weight of the above-mentioned carboxyl group-containing resin varies with the resin skeleton, but is preferably in the range of 2,000 to 150,000, and more preferably in the range of 5,000 to 100,000. If the weight average molecular weight is within this range, the tack-free performance is good, the moisture resistance of the coating film after exposure is good, the developability or resolution, and the storage stability are excellent. The blending amount of these carboxyl group-containing resins in the curable composition (solid content) is 20% by mass to 80% by mass, preferably 30% by mass to 70% by mass. If the blending amount of the carboxyl group-containing resin is within this range, the strength of the coating film will not decrease, and it will not cause viscosity increase or decrease in workability.

Moreover, in this invention, as (A) alkali-soluble resin, either a photosensitive carboxyl group containing resin and the carboxyl group containing resin which does not have photosensitivity can be used, You may mix and use these.

The phenol resin is a compound having a phenolic hydroxyl group, for example, a compound having a biphenyl skeleton or a phenylene skeleton or both skeletons, or a compound containing a phenolic hydroxyl group such as phenol, o-cresol, p-cresol, M-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-dimethylphenol Phenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, Phenolic resin with various skeletons synthesized by phloroglucinol.

For example, phenol novolak resin, alkylphenol novolak resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene-modified phenol resin, polyvinyl phenols, bisphenols can be used. F. Known and commonly used phenol resins such as bisphenol S-type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxy naphthalene and aldehydes.

These can be used individually or in combination of 2 or more types.

Examples of commercially available products of the phenol resin include HF-1M (manufactured by Meiwa Chemical Co., Ltd.), Phenolite TD-2090, Phenolite TD-2131 (manufactured by DIC Corporation), Besmol CZ-256-A (manufactured by DIC Corporation), Shonol BRG-555, Shonol BRG-556 (manufactured by AICA), CGR-951 (manufactured by Maruzen Oil Co.), or polyvinylphenol CST70, CST90, S-1P, S-2P (manufactured by Maruzen Oil Co.), etc. These phenol resins can be used individually or in combination of 2 or more types.

[(B) Photopolymerization initiator] (B) The photopolymerization initiator is added to start radical polymerization of ethylenic unsaturated groups by irradiation of energy rays.

(B) Examples of photopolymerization initiators are benzidine and benzyl ethers such as benzyl, benzyl methyl ether, benzyl ether, and benzyl isopropyl ether; acetophenone, 2 , 2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, Acetophenones such as 1,1-dichloroacetophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-one, 2-benzyl- 2-Dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1- [4-(4-morpholinyl)phenyl]-1-butanone and other amino benzophenones; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, Anthraquinones such as 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone Thioxanthones such as ketones; acetals such as acetophenone dimethyl acetal and benzyl dimethyl acetal; 4,4'-bis(diethylamino)benzophenones and other diphenyl ketones Methyl ketones; (2,6-dimethoxybenzyl)-2,4,4-pentyl phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenyl oxide Phosphine, 2,4,6-trimethylbenzyl diphenyl phosphine oxide, 2,4,6-trimethylbenzyl phenyl phosphinic acid ethyl ester, etc.; 1,2 -Octanedione, 1-[4-(phenylthio)-,2-(O-benzyloxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl) (Acetyl)-9H-carbazol-3-yl]-,1-(O-acetoxime) and other oxime esters; various peroxides, titanocene-based initiators, etc. These can also be combined with ethyl N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, pentyl 4-dimethylaminobenzoate, triethylamine, triethanolamine The third-level amine light sensitizer, etc. are used together. These photopolymerization initiators can be used alone or in combination of two or more kinds.

(B) The blending amount of the photopolymerization initiator, in the curable composition of the present invention, is in the range of 0.01 parts by mass to 30 parts by mass relative to 100 parts by mass (solid content) of (A) alkali-soluble resin It is better to mix in the range of 0.5 parts by mass to 20 parts by mass.

[(C) Epoxy] (C) The epoxy resin is a compound added in order to thermally harden the curable composition of the present invention.

(C) The epoxy resin can be a conventionally used polyfunctional epoxy resin having at least two epoxy groups in one molecule. Examples of (C) epoxy resins include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, EPICLON 840, EPICLON 850, EPICLON 850-S, EPICLON 1050, EPICLON 2055 manufactured by Toto Kasei Co., Ltd. manufactured by DIC Corporation EPOTOT YD-011, YD-013, YD-127, YD-128, DER317, DER331, DER661, DER664 manufactured by Dow Chemical Company, Sumi-epoxy ESA-011, ESA-014 manufactured by Sumitomo Chemical Industry Company , ELA-115, ELA-128, etc. (all trade names) of bisphenol A epoxy resin; jER YL903 manufactured by Mitsubishi Chemical Corporation, EPICLON 152 and EPICLON 165 manufactured by DIC Corporation, and EPOTOT YDB- manufactured by Toto Kasei Corporation 400, YDB-500, DER542 made by Dow Chemical Company, Sumi-epoxy ESB-400, ESB-700 made by Sumitomo Chemical Industries, etc. (all trade names) brominated epoxy resin; jER made by Mitsubishi Chemical Company 152. jER 154, DEN431 and DEN438 manufactured by Dow Chemical Company, EPICLON N-730, EPICLON N-770, EPICLON N-865 manufactured by DIC, EPOTOT YDCN-701, YDCN-704 manufactured by Toto Kasei, Japan EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000 manufactured by Chemical Pharmaceuticals, Sumi-epoxy ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Industries, Nippon Steel Chemical YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704A manufactured by the company, EPICLON N-680 manufactured by DIC Novolac epoxy resins such as EPICLON N-690 and EPICLON N-695 (both trade names); EPICLON 830 manufactured by DIC, jER 807 manufactured by Mitsubishi Chemical Corporation, EPOTOT YDF-170, YDF manufactured by Toto Kasei -175, YDF-2004, etc. (all trade names) bisphenol F type epoxy resin; EPOTOT ST-2004, ST-2007, ST-3000 (trade names) manufactured by Toto Kasei Corporation, YX8034 manufactured by Mitsubishi Chemical Corporation Hydrogenated Bisphenol A Epoxy Resin; JER 604 manufactured by Mitsubishi Chemical Corporation, Dongdu EPOTOT YH-434 manufactured by Kasei Co., Ltd.; Glycidylamine epoxy resin such as Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Industry Co. (all trade names); Hydantoin-type epoxy resin; Dicel Chemical Industry Co., Ltd. Alicyclic epoxy resins such as Celloxide 2021 (all trade names) manufactured by Mitsubishi Chemical Corporation, EPPN-501 and EPPN-502 manufactured by Nippon Kayaku Co., Ltd. (all trade names) Hydroxyphenylmethane type epoxy resin; YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation, etc. bis-xylenol type or diphenol type epoxy resin or mixtures of these EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA, EXA-1514 (trade name) manufactured by DIC, etc. Bisphenol S-type epoxy resin; jER 157S (trade name) manufactured by Mitsubishi Chemical Corporation ) And other bisphenol A novolac type epoxy resin; JER YL-931, etc. (all trade names) manufactured by Mitsubishi Chemical Corporation; tetrahydroxyphenylethane type epoxy resin; Blenmer DGT manufactured by Nippon Oil & Fat Co., Ltd. Diglycidyl phthalate resin; Heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industry Co., Ltd. (all trade names); Tetraglycidyl xylene such as ZX-1063 manufactured by Toto Kasei Co., Ltd. Ethane resin; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Corporation, HP-4032, EXA-4750, EXA-4700 manufactured by DIC Corporation, etc. naphthyl-containing epoxy resin; manufactured by DIC Corporation Epoxy resins with dicyclopentadiene skeletons such as HP-7200 and HP-7200H; glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M manufactured by NOF Corporation; and There are copolymerized epoxy resins of cyclohexyl maleimide and glycidyl methacrylate; CTBN modified epoxy resins (such as YR-102, YR-450 manufactured by Toto Kasei Co., Ltd.), etc., but not Limited to these.

When the (C) epoxy resin is blended, it is blended so that the carboxylic acid equivalent of the alkali-soluble resin (A) is 0.8 epoxy equivalent or more and 2.0 epoxy equivalent or less. The carboxylic acid equivalent here means the weight of (A) alkali-soluble resin necessary to obtain 1 mole of carboxyl group, and the unit is g/mol. In addition, the epoxy equivalent means the weight of (C) epoxy resin necessary to obtain 1 mole of epoxy group, and the unit is g/mol. (C) The mass of the epoxy resin is 0.8 epoxy equivalent or more and 2.0 epoxy equivalent or less with respect to the carboxylic acid equivalent of (A) alkali-soluble resin. When the epoxy equivalent is within these ranges, a cured product with excellent heat resistance, electrical properties, and crack resistance can be obtained.

[(D) Polysiloxane compound] (D) The polysiloxane compound is formulated in order to improve the wettability of the curable composition of the present invention to the copper-clad substrate (base material), suppress non-sticking, and improve leveling properties.

(D) The polysiloxane compound is polydimethylsiloxane or a derivative with polydimethylsiloxane as the basic structure, for example, polydimethylsiloxane, polyether modified polydimethylsiloxane Oxyane, polyester modified polydimethylsiloxane, polyester modified polymethylalkylsiloxane, polyether modified polymethylalkylsiloxane, aralkyl modified polymethylsiloxane Base silicone, polyether modified silicone, polyester modified polydimethylsiloxane with hydroxyl group, etc.

Examples of commercially available products as (D) polysiloxane compounds are BYK (registered trademark) -300, BYK (registered trademark) -302, BYK (registered trademark) -306, BYK (registered trademark) -307, BYK (registered trademark) ) -310, BYK (registered trademark) -315N, BYK (registered trademark) -320, BYK (registered trademark) -322, BYK (registered trademark) -323, BYK (registered trademark) -325, BYK (registered trademark)- 330, BYK (registered trademark) -331, BYK (registered trademark) -333, BYK (registered trademark) -342, BYK (registered trademark) -345, BYK (registered trademark) -346, BYK (registered trademark) -347, BYK (registered trademark) -348, BYK (registered trademark) -349, BYK (registered trademark) -370, BYK (registered trademark) -377, BYK (registered trademark) -378, BYK (registered trademark) -3455 (the above are Japan BYK Corporation).

(D) In the curable composition of the present invention, the polysiloxane compound is in the range of 0.1 parts by mass to 10 parts by mass relative to 100 parts by mass (solid content) of (A) alkali-soluble resin, preferably 1 part by mass Blended in the range of more than 5 parts by mass. By making the (D) polysiloxane compound in the range of 0.1 parts by mass to 10 parts by mass, the wettability of the curable composition to the copper-clad substrate (base material) can be ensured, the leveling properties are good, and the flux is The wettability of the hardened material also becomes good.

[(E) Hydrophilic silica] (E) Hydrophilic silica is added to suppress the curing shrinkage of the curable composition of the present invention and to strengthen the rigidity of the resulting cured product.

In the present invention, the so-called (E) hydrophilic silica refers to untreated silica that has not been subjected to surface treatment to add a hydrophobic organic group to its hydrophilic surface. Examples are molten silica, spherical silica, Amorphous silicon dioxide, crystalline silicon dioxide, etc.

In addition, the so-called surface treatment for adding hydrophobic organic groups refers to treatment (untreated) with a coupling agent having hydrophobic organic groups such as ethylenic unsaturated groups (photocurable reactive groups), alkyl groups, etc. The surface of silicon oxide, the surface-treated silicon oxide is not included in the above-mentioned (E) hydrophilic silicon dioxide.

Examples of commercially available products are FB-15D, FB-105, FB-105X, FB-5SDX, SFP-20M, SFP-130MC (the above are manufactured by Denki Kogyo Co., Ltd.), EXCELICA (registered trademark) (Tokuyama Co., Ltd. Corporation), SR-NP (M.TEC Chemical Corporation), etc.

(E) When the hydrophilic silica is used to form the cured film of the printed wiring board, the median diameter (D50) is less than 30μm, and the cured film on the IC package substrate is less than 5μm, the median diameter (D50) When it is in the range of 0.2 μm or more and 2 μm or less, it is preferable from the viewpoint of dispersibility in the curable composition. In addition, the method for measuring the median diameter (D50) is as follows.

＜Measuring method of median diameter (D50)＞ Put 30ml of ethanol and 1g of silicon dioxide powder into a 100ml beaker, stir in a desktop ultrasonic cleaner for 3 minutes, and then use a laser diffraction/scattering particle size analyzer (manufactured by MICROTRAC BEL) MICROTRAC MT-3300, measure the volume-based median diameter (D50) in ethanol solvent.

In addition, (E) hydrophilic silica in the curable composition of the present invention preferably ranges from 10 parts by mass to 200 parts by mass relative to 100 parts by mass (solid content) of (A) alkali-soluble resin It is formulated in the range of 20 parts by mass to 180 parts by mass. By making (E) hydrophilic silica in the range of 10 parts by mass or more and 200 parts by mass or less, curing shrinkage suppression and rigidity strengthening effects of the cured product can be obtained, and the dispersibility is also good.

[(F) Organic thixotropic agent] (F) The organic thixotropic agent is used to inhibit the aggregation and precipitation of (E) hydrophilic silica in the curable composition of the present invention, and, as the present invention firstly understood, to improve the hardening of the flux to the present invention It is added for the wettability of the cured product of the sexual composition.

The (F) organic thixotropic agent that can be used in the curable composition of the present invention includes fatty acid amides (aramide waxes) synthesized from vegetable oil fatty acids and amines; fatty acid esters, polyethers, and sulfated Surfactants such as oils, higher alcohol sulfate esters; polycarboxylates; polycarboxylates; urea modification compounds, but excluding hydrogenated castor oil series called castor oil waxes and polyethylene Oxidation treatment of the oxidized polyethylene series of wax with polar groups.

Examples of commercially available products as (F) organic thixotropic agents are BYK (registered trademark)-R606, BYK (registered trademark)-405, BYK (registered trademark)-R605, BYK (registered trademark)-R607, BYK (registered trademark) ) -410, BYK (registered trademark) -411, BYK (registered trademark) -415, BYK (registered trademark) -430, BYK (registered trademark) -431, BYK (registered trademark) -7410ET, BYK (registered trademark)- 7411ES (the above are made by BYK Japan), TALEN 1450, TALEN 2000, TALEN 2200A, TALEN 7200-20, TALEN 8200-20, TALEN 8300-20, TALEN 8700-20, TALEN BA-600, FLOWNON SH-290, FLOWNON SH-295S, FLOWNON SH-350, FLOWNON HR-2, FLOWNON HR-4AF (the above are manufactured by Kyoeisha Chemical Co., Ltd.).

(F) Organic thixotropic agent in the curable composition of the present invention, relative to 100 parts by mass (solid content) of (E) hydrophilic silica is 0.01 parts by mass or more and 15 parts by mass or less, preferably 0.05 parts by mass Above 10 parts by mass or less.

In addition, the (F) organic thixotropic agent is 0.05 parts by mass or more, preferably 0.1 parts by mass or more, relative to 2 parts by mass of the (D) polysiloxane in the curable composition of the present invention.

By being within the above-mentioned range, (E) hydrophilic silica is well dispersed, and the wettability of the flux to the cured product of the curable composition is also good.

[(G) Antioxidant] It is preferable to add (G) antioxidant to the curable composition of the present invention. (G) Antioxidant improves the adhesion between the substrate and the curable composition by suppressing the oxidation of copper on the copper-clad substrate (substrate).

Examples of (G) antioxidants include hindered phenol compounds such as 3-(N-salicylenyl)amino-1,2,4-triazole, sulfur-based antioxidants such as zinc salts of 2-mercaptobenzimidazole, three Phosphorus antioxidants such as phenylphosphine, aromatic amine antioxidants such as di-tert-butyldiphenylamine, melamine, benzotriazole, tolyltriazole, etc., heterocyclic type containing nitrogen as a heteroatom Compounds (except sulfur-based antioxidants), etc. Among them, melamine is preferred.

(G) The compounding amount of antioxidant, in the curable composition of the present invention, relative to 100 parts by mass (solid content) of (A) alkali-soluble resin is 0.1 parts by mass or more and 5 parts by mass or less, preferably 0.5 parts by mass The above 2 parts by mass or less.

[Other ingredients] Furthermore, it is preferable to add a photopolymerizable polyfunctional monomer to the curable composition of the present invention. A photopolymerizable multifunctional mono-system compound having two or more ethylenic unsaturated groups in one molecule, (in the case of (A) alkali-soluble resin containing ethylenic unsaturated groups) helps to activate The energy ray is irradiated to photocur the (A) alkali-soluble resin, and it is used for photocuring the curable composition.

Examples of compounds used as photopolymerizable polyfunctional monomers are, for example, conventionally known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, and carbonates. (Meth)acrylate, epoxy (meth)acrylate, etc. Specific examples are polyols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tri-hydroxyethyl isocyanurate, etc. or their ethylene oxide adducts and propylene oxide adducts , Or ε-caprolactone adducts and other polyacrylates; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide additions of these phenols Polyacrylates such as glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate and other glycidyl ether polyacrylates; Not limited to the foregoing, but polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, etc., are directly acrylated, or urethane acrylates via diisocyanate groups At least any one of acrylates and melamine acrylates, and methacrylates corresponding to the aforementioned acrylates.

In the curable composition of the present invention, the photopolymerizable polyfunctional monomer is in the range of 3 parts by mass to 30 parts by mass relative to 100 parts by mass (solid content) of (A) alkali-soluble resin, preferably 10 parts by mass It is formulated in the range of 20 parts by mass or less.

The curable composition of the present invention preferably further contains a curing catalyst such as dicyanodiamide, boron trifluoride-amine catalyst, and organic acid hydrazine. In the curable composition of the present invention, the curing catalyst is added in an amount of 5 parts by mass or less, preferably in the range of 0.1 parts by mass to 2 parts by mass relative to 100 parts by mass (solid content) of (A) alkali-soluble resin .

Furthermore, in the curable composition of the present invention, coloring pigments, dyes, etc. may be added for the purpose of coloring. As coloring pigments, dyes, etc., conventional ones expressed by color index can be used. Examples are Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122 , 136, 67, 70, pigment green 7, 36, 3, 5, 20, 28, solvent yellow 163, pigment yellow 24, 108, 193, 147, 199, 202, 110, 109, 139, 179, 185, 93 , 94, 95, 128, 155, 166, 180, 120, 151, 154, 156, 175, 181, 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1 , 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183, 12, 13, 14, 16, 17, 55, 63, 81, 83, 87 , 126, 127, 152, 170, 172, 174, 176, 188, 198, Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51 , 61, 63, 64, 71, 73, Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112 , 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269, 37, 38, 41, 48: 1, 48: 2, 48 :3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2 , 64: 1, 68, 171, 175, 176, 185, 208, 123, 149, 166, 178, 179, 190, 194, 224, 254, 255, 264, 270, 272, 220, 144, 166, 214 , 220, 221, 242, 168, 177, 216, 122, 202, 206, 207, 209, solvent red 135, 179, 149, 150, 52, 207, pigment violet 19, 23, 29, 32, 36, 38 , 42, Solvent Violet 13, 36, Pigment Brown 23, 25, Pigment Black 1, 7, etc. The coloring pigments. Dyes and the like can be added in an amount ranging from 0.01 part by mass to 5 parts by mass, preferably 0.1 part by mass to 3 parts by mass, relative to 100 parts by mass of the curable composition.

Furthermore, if necessary, conventionally used polymerization inhibitors, photopolymerization sensitizers, photopolymerization sensitizers, etc., can be adjusted according to needs, such as hydroquinone, hydroquinone monomethyl ether, tertiary butylcatechol, pyrogallol, phenothiazine, etc. Commonly used additives such as light stabilizers, flame retardants, flame retardant additives.

In addition, the curable composition of the present invention may also contain an organic solvent for adjusting the viscosity. As organic solvents, ketones such as methyl ethyl ketone and cyclohexanone can be used; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbamide Alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (DPM), dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether and other glycol ethers; ethyl acetate, acetic acid Butyl ester, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Esters such as acetate and propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum-based solvents such as petroleum ether, naphtha, and solvent naphtha. These organic solvents can be used individually or in combination of 2 or more types.

<The dry film and cured product of the curable composition of the present invention> The curable composition of the present invention can be coated on a carrier film (support) and dried to obtain a dry film form. When the film is dried, the curable composition of the present invention is diluted with the above-mentioned organic solvent to adjust it to an appropriate viscosity, and it is coated with a chipped wheel coater, knife coater, lip die coater, rod coater, and rubber roller. Cloth device, reverse roll coater, conveyor roll coater, gravure coater, spray coater, etc., coat the carrier film with a uniform thickness, usually, dry at a temperature of 50 to 130 ℃ for 1 to 30 minutes, A dry coating film can be obtained. The coating film thickness is not particularly limited, but the film thickness after drying is generally 0.1-100 μm, preferably the range of 0.5-50 μm is appropriately selected.

As the carrier film, plastic film is used, such as polyester film such as polyethylene terephthalate, polyimide film, polyimide film, polypropylene film, polystyrene film, etc. . The thickness of the carrier film is not particularly limited, but is generally selected appropriately within the range of 0.1 to 150 μm.

In this case, after the coating film is formed on the carrier film, it is preferable to laminate a peelable cover film on the coating film surface for the purpose of preventing dust from adhering to the surface of the coating film. The peelable cover film can use, for example, polyethylene film or polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc., as long as the adhesion between the coating film and the cover film is less than that of the coating film and the carrier film when the cover film is peeled off Then force it.

In addition, the curable composition of the present invention is adjusted to a viscosity suitable for the coating method using the above-mentioned organic solvent, and then applied to the substrate by dip coating, flow coating, roll coating, or bar coating. Coating by cloth method, screen printing method, curtain coating method, die nozzle coating method, etc., at about 50℃~ The temperature of 90℃ makes the organic solvent contained in the composition volatilize and dry (temporarily dry), and a dry coating film without tackiness can be formed. In addition, when the curable composition of the present invention is applied to a carrier film and then dried to form a dry film that is rolled up, the coating film of the curable composition is brought into contact with the substrate by a laminator or the like After being attached to the substrate, the carrier film is peeled off, thereby forming a coating film layer on the substrate.

The coating films can be photocured by irradiation with active energy rays, or thermally cured by heating to a temperature of 100°C to 250°C to obtain a cured product.

The above-mentioned substrate can be exemplified by a printed wiring board or a flexible printed wiring board with pre-formed circuits, in addition to paper + phenol resin, paper + epoxy resin, paper + glass cloth + epoxy resin, glass non-woven fabric + epoxy resin, Glass woven cloth + epoxy resin, glass fiber + polyimide resin and other copper-clad laminates.

After coating the curable composition of the present invention, the volatile drying can be carried out by using a hot air circulating drying furnace, IR furnace, hot plate, forced oven, etc., which has a heat source that uses steam air heating to make the hot air in the dryer contact convectively The method and the method of using the nozzle to blow the support body.

As the exposure machine used for the above-mentioned active energy ray irradiation, if it is equipped with a high-pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, mercury arc lamp, etc., the device irradiates ultraviolet rays in the range of 350 to 450 nm, and direct drawing Devices (such as direct imaging devices that draw images by directly irradiating active energy rays from CAD data from a computer). As the light source of the direct drawing machine, as long as the maximum wavelength is in the range of 350~410nm. The amount of exposure used for image formation varies with the film thickness, etc., but is generally 20 to 1000 mJ/cm ² , preferably in the range of 20 to 800 mJ/cm ² .

In addition, as a developing method, dipping, rinsing, spraying, brushing, etc. can be used. As a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, and sodium silicate can be used. , Ammonia, amines and other alkaline aqueous solutions.

In this way, the dry film and cured product obtained from the curable composition of the present invention can be applied to various applications due to its excellent heat resistance, rigidity, adhesion to the substrate, and insulation, and the applicable object is not particularly limited. For example, it can be used for etching resists, solder resists, and standard resists for the production of printed wiring boards. Among them, since solderability is improved, it can be preferably used as a solder resist that requires high heat resistance.

<Electronic parts that use the cured product of the curable composition as the insulating cured film> When the cured product of the curable composition patterned on the substrate is used as a solder resist, it is heated in the soldering step for component mounting. Hand welding can be performed by either flow welding or reflow welding. For example, during reflow welding, it is used for preheating at 100℃~140℃ for 1~4 hours, and then heating at 240℃~280℃5 Repeat the reflow step of heating and melting several times (for example, 2~4 times) for about 20 seconds. After cooling, install the parts as needed to complete the electronic parts.

Examples are shown below to specifically illustrate the present invention, but the present invention is not limited to these examples. In addition, as long as there is no particular limitation below, "parts" means parts by mass. [Example]

(Synthesis of alkali-soluble resin) [Synthesis Example 1] After dissolving 380 parts of bisphenol F epoxy resin (epoxy equivalent 950g/eq, softening point 85°C) and 925 parts of epichlorohydrin in 462.5 parts of dimethyl sulfoxide, add 98.5 at 70°C for 100 minutes while stirring %NaOH 60.9 parts. After the addition, the reaction was further carried out at 70°C for 3 hours. After the reaction, 250 parts of water was added and washed with water. After separation of oil and water, most of the dimethyl sulfide and excess unreacted epichlorohydrin are recovered from the oil layer under reduced pressure. The remaining reaction product containing by-product salt and dimethyl sulfide is dissolved in methyl isobutyl ketone 750 In addition, 10 parts of 30% NaOH was further added, and reacted at 70°C for 1 hour. After the reaction, it was washed twice with 200 parts of water. After the oil and water are separated, the methyl isobutyl ketone is distilled and recovered from the oil layer to obtain an epoxy resin (a) with an epoxy equivalent of 310 g/eq and a softening point of 69°C. If the obtained epoxy resin (a) is calculated from the epoxy equivalent, about 5 of the 6.2 alcoholic hydroxyl groups in the bisphenol F epoxy resin of the starting material are epoxidized. 310 parts of the epoxy resin (a) and 282 parts of carbitol acetate were put into a flask, heated at 90°C, stirred and dissolved. The resulting solution was temporarily cooled to 60°C, 72 parts of acrylic acid (1 mol), 0.5 part of methylhydroquinone, and 2 parts of triphenylphosphine were added, heated to 100°C, and reacted for about 60 hours to obtain an acid value of 0.2mgKOH/ The reactant of g. 140 parts (0.92 mol) of dry tetrahydrophthalic acid was added to it, and the reaction was carried out by heating to 90°C to obtain a photosensitive carboxyl group-containing resin varnish (A-1). The solid content concentration of the obtained carboxyl group-containing resin varnish (A-1) was 62.5%, and the solid content acid value (mgKOH/g) was 100.

[Synthesis Example 2] Cresol novolac type epoxy resin (manufactured by Dainippon Ink Chemical Industry Co., Ltd., registered trademark "EPICLON" N-695, epoxy equivalent: 220) 220 parts are fed into a four-necked flask with a mixer and a sulfur return cooler In, 214 parts of carbitol acetate was added and heated to dissolve. Next, add 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of dimethylbenzylamine as a reaction catalyst. The mixture was heated at 95-105°C, 72 parts of acrylic acid was slowly added dropwise, and reacted for 16 hours. The reaction product was cooled to 80 to 90°C, 106 parts of tetrahydrophthalic anhydride was added, and reacted for 8 hours, and then taken out after cooling. The thus obtained photosensitive resin having both ethylenic unsaturated bonds and carboxyl groups has a non-volatile content of 65%, an acid value of a solid content of 85 mgKOH/g, and a weight average molecular weight Mw of approximately 3,500. Hereinafter, this resin solution is referred to as varnish (A-2). In addition, the weight-average sub-quantity of the obtained resin was measured by a high-speed liquid chromatograph connected with three pumps LC-804, KF-803, and KF-802 manufactured by Shimadzu Corporation.

<1. Preparation of curable compositions of Examples 1 to 9 and Comparative Examples 1 to 3> The resin solution of the example and the materials shown in Table 1 were separately blended, premixed with a mixer, and then kneaded with three roll mills to prepare a curable composition. In Table 1, (A-1) to (A-3) represent the parts by mass of the resin solution each containing a solvent.

The following characteristic tests were performed on each of the above-mentioned compositions. The results are shown in Table 1.

＜2. Evaluation of non-sticking and leveling property of hardened hard composition to substrate＞ On the copper-clad substrate (base material) whose surface is roughened by chemical polishing, use a screen (Tetlon 100 mesh) to harden <1. Examples 1-9 and Comparative Examples 1~3 Preparation of the sexual composition> Each curable composition adjusted in the middle is printed on the entire surface of the copper-clad substrate to have a thickness of 10μm.

Visually observe the coating film immediately after printing to confirm whether the curable composition does not stick and the leveled state (smoothness). Next, the printed circuit board was dried at 80°C for 30 minutes, and after returning to room temperature, the state of the coating film after drying was also visually confirmed. (Also, although visual confirmation was performed in this example, when visual judgment is difficult, a surface roughness measuring machine (SurfCorder: manufactured by Kosaka Laboratory Co., Ltd.) or a shape measuring laser microscope (VK-X-100 /KEYENCE Corporation) Observe surface roughness). The evaluation criteria are as follows.

○: No sticking, no trace of screen △: There is no sticking and no traces of the screen, or no sticking and there are traces of the screen ×: There is no sticking, and there are traces of screen

＜3. Evaluation of non-sticking flux＞ Using a screen (Tetlon 100 mesh), print each curable composition adjusted in <1. Preparation of curable composition of Examples 1 to 4 and Comparative Examples 1 to 4> by chemical polishing The FR-4, 35μm thick copper-clad substrate with a rough surface of 150×95mm and a thickness of 1.6mm is made to have a film thickness of 10μm.

After drying at 80°C for 30 minutes, use a 95×150mm exposure mask to form a pattern to expose at 600mJ/cm ² and perform alkali development (1% Na ₂ CO ₃ aqueous solution, 30°C, 60 seconds development ), after heat curing at 150°C/60 minutes, UV treatment is performed after 1000mJ/cm ² .

Electroless Sn plating (Sn: 1.1μm/ Tsukada Riken Kogyo Co., Ltd.) is applied to the FR-4 substrate (base material) on which the hardened product of the curable composition is fixed, and the reflow step is repeated 1 to 3 times (265°C), before the reflow step after the electroless Sn plating treatment, after the reflow step once, after the reflow step 2 times, and after the reflow step 3 times, the hardening of the fixed hardenable composition The FR-4 substrate of the material was subjected to a wet tension test.

Wetting tension test is based on JIS K6768. As a mixture for wetting tension test, use "mixture for wetting tension test No. 60.0" before reflow step after electroless Sn plating treatment, and use it after 1 reflow step. "Mixture for Wetting Tension Test No. 38.0", use "Mixture for Wetting Tension Test No. 36.0" after 2 reflow steps, and use "Mixture for Wetting Tension Test No. 34.0" after 3 reflow steps ". Any mixture for the wet tension test is manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. The NO. of each mixed liquid represents the surface tension of the mixed liquid (unit: mN/m).

Specifically, the wetting tension test is drawn with a cotton swab with the mixed liquid for the wetting tension test, and the state of the liquid film after 2 seconds is observed. In addition, when the liquid film did not crack and remained in the coating state for more than 2 seconds, it was judged to be wet.

In addition, the higher the value of the mixed solution for the wetting tension test, the better the flux non-stickiness. Therefore, the wetting tension test was used as a test to evaluate the flux non-stickiness.

In Table 1, the evaluation criteria are as follows.

○: After the electroless Sn plating process, before the reflow step to after the reflow step 3 times, it is judged that there is wetting (no non-sticking).

×: After the electroless Sn plating process, before the reflow step ~ after the reflow step 3 times, it may be judged that there is no moisture (non-sticking) once.

*1: CYCLOMER P(ACA) Z250 (Solid content of 45wt% of unsaturated group-containing carboxyl group-containing copolymer resin solution, manufactured by DAICEL Chemical Company) *2: 2,4,6-trimethylbenzyl diphenyl phosphine oxide (Omnirad TPO H: manufactured by IGM Resins B.V.) *3: 2-Dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one (Omnirad 379: IGM Resins BV) system) *4: Bisphenol A epoxy resin (JER (registered trademark)-834: manufactured by Mitsubishi Chemical Corporation) *5: Triglycidyl isocyanurate (TEPIC-HP: manufactured by Nissan Chemical Industry Co., Ltd.) *6: Polyester modified polydimethylsiloxane (BYK (registered trademark)-313: manufactured by BYK Japan) *7: Polyether modified polydimethylsiloxane (BYK (registered trademark)-300: manufactured by BYK Japan) *8: Spherical silicon dioxide (D50=0.6μm) (SFP-130MC: manufactured by Denki Kagaku Kogyo) *9: Spherical silicon dioxide (D50=0.4μm) (SFP-20M: manufactured by Denki Kagaku Kogyo) *10: Polyhydroxy carboxylate (BYK (registered trademark)-R 606: manufactured by BYK Japan) *11: Melamine (Melamine: manufactured by Nissan Chemical Industry Co., Ltd.) *12: Spherical silicon dioxide (1.5μm SM-C4: manufactured by ADOMATEX) whose surface has been treated with methacrylic alkane *13: Dipentaerythritol hexaacrylate (DPHA: manufactured by Nippon Kayaku Co., Ltd.) *14: Dicyanodiamide (C0454: manufactured by Tokyo Chemical Industry Co., Ltd.) *15: Blue pigment (Fastogen Blue-5380: manufactured by DIC), Table 1 shows the mass of solid content *16: Yellow pigment (Cromophtal (registered trademark) Yellow S1515: manufactured by BASF Corporation). Table 1 shows the mass of solid content *17: Dipropylene glycol methyl ether (Dowanol (registered trademark) DPM: manufactured by Dow Chemical Co., Ltd.)

As shown in the examples in Table 1, when (D) polysiloxane compound, (E) hydrophilic silica and (F) organic thixotropic agent are formulated, the curable composition of the present invention is maintained on the copper-clad substrate ( The wettability and leveling properties of the substrate) are also good, and (E) the hydrophilic silica does not aggregate or precipitate. In addition, when the mixture for wet tension test was applied to the substrate on which the cured product of the curable composition of the present invention was fixed, the mixture for wet tension test was not adhered to the cured product, and the wet tension test was maintained The wettability of the hardened substance with the mixture.

On the other hand, in Comparative Example 1 in which a hydrophobic treatment was applied to the surface of silicon dioxide, even if (F) an organic thixotropic agent was formulated, the mixed solution for the wetting tension test had an effect on the base of the hardened product fixed with the hardenable composition of the present invention. The wettability of the material is still reduced, and the weldability is considered to be reduced. In addition, in Comparative Example 2 which does not contain (F) organic thixotropic agent, even if (D) polysiloxane compound and (E) hydrophilic silica are blended, the mixture for wet tension test is fixed with the curable composition of the present invention The wettability of the base material of the hardened material is still reduced, and it is considered that the weldability is reduced. Furthermore, in Comparative Example 3 which did not contain the (D) polysiloxane compound, the wettability of the curable composition to the copper-clad substrate (base material) was insufficient, or the leveling property was deteriorated.

Claims (7)

A sclerosing composition characterized by (A) Alkali-soluble resin, (B) photopolymerization initiator, (C) epoxy resin, (D) Polysiloxane compound, (E) Hydrophilic silica, and (F) Organic thixotropic agent. Such as the curable composition of claim 1, wherein (E) the median diameter D50 of the hydrophilic silica is 0.2 μm or more and 2.0 μm or less. Such as the curable composition of claim 1 or 2, wherein the amount of (F) organic thixotropic agent is 0.01 parts by mass to 15 parts by mass relative to 100 parts by mass of (E) hydrophilic silica, and is relative to (D) 2 parts by mass of polysiloxane compound, 0.05 parts by mass or more. The curable composition according to any one of claims 1 to 3, which further contains (G) an antioxidant. A dry film characterized by coating the curable composition of any one of claims 1 to 4 on a carrier film and drying it. A cured product characterized by coating the curable composition of any one of claims 1 to 4 on a substrate and drying the dried coating film obtained by curing, or applying the aforementioned curable composition to The coating film formed by laminating the dry film on the carrier film and drying on the substrate is obtained by curing. An electronic component characterized by being provided with a hardened object as in Claim 6.