KR20230061448A - Photocurable thermosetting resin composition, dry film, cured product, and electronic component having the cured product - Google Patents

Abstract

[Problem] To provide a photocurable thermosetting resin composition that is excellent in storability, suppresses problems such as pinholes and crawling in the resulting dry film, and also has excellent electrical properties, a cured product thereof, and an electronic component having the cured product. do. [Solution] A photocurable thermosetting resin composition containing (A) an epoxy resin, (B) a carboxyl group-containing resin, (C) a photopolymerization initiator, (D) a photosensitive monomer, (E) silica, (F) barium sulfate and an organic solvent. In order to obtain the photocurable thermosetting resin composition, it is composed of at least a two-component resin composition, and the (B) carboxyl group-containing resin, the (D) photosensitive monomer, and the (E) silica are the (A) epoxy resin, It is contained in a resin composition different from the barium sulfate (F) and the photopolymerization initiator (C), and the resin composition containing the photopolymerization initiator (C) contains an organic solvent capable of dissolving the photopolymerization initiator (C). A photocurable thermosetting resin composition composed of at least a two-component resin composition, a cured product obtained from the curable composition, and an electronic component having the cured product.

Description

Photocurable thermosetting resin composition, dry film, cured product, and electronic component having the cured product

The present invention relates to a photocurable thermosetting resin composition, a dry film, a cured product, and an electronic component having the cured product. In particular, the present invention relates to a photocurable thermosetting resin composition comprising at least a two-liquid system and a cured product thereof suitable for a printed wiring board, such as a solder resist, and an electronic component having the cured product.

Conventionally, in a printed wiring board, a solder resist is used as a protective material for a wiring board circuit, and high solder heat resistance and electrical insulation properties are required. As an example of the material composition, for example, an alkali developing type photocurable thermosetting resin composition can

As a component of such a photocurable thermosetting resin composition, a photosensitive polymer having a carboxyl group is mainly contained as a material, but an epoxy resin may be further contained in order to improve the solder heat resistance of the cured product obtained after curing the composition. By the way, since an epoxy resin reacts relatively easily with the photosensitive polymer which has a carboxyl group, it has a subject in long-term storage as a composition. Therefore, in general, a method of preparing a photocurable thermosetting resin composition by mixing easily reactive components in a two-liquid system in a separate composition and mixing them at the time of use has been used.

Japanese Patent No. 5688116

In recent years, however, the density of printed wiring boards has been remarkably increased, and the circuit has a minimum line of 10 μm and a space of 10 μm, and insulation reliability higher than before is required. Due to the high density of this printed circuit board, insoluble substances (such as inorganic fillers and crystalline epoxy resins) exist as particles between fine pattern circuits, causing short circuits between circuits.

In addition, in the case where a dry film was produced by applying and drying a two-component photocurable thermosetting resin composition on a carrier film, after mixing each of the two-component resin compositions stored for one month after production, it was applied to the carrier film. At this time, crawling or pinholes occur due to coarse particles that are thought to have occurred during the storage period of those resin compositions stored in separate containers, and there is also a problem in long-term storage stability.

On the other hand, for example, Patent Literature 1, among the constituent components of the photocurable thermosetting resin composition, pays attention to the epoxy resin and discloses preventing the generation of these coarse particles.

However, as described above, the high density of the printed wiring board is remarkable, and in the photocurable thermosetting resin composition, higher insulation reliability is required, suppressing the generation of coarse particles due to various factors in addition to the epoxy resin, electrical properties ( HAST resistance) is required to further improve.

In addition, from the viewpoint of securing stock, even when one month has elapsed after the production of each resin composition, generation of coarse particles caused by various factors as well as epoxy resin is suppressed, and crawling and pinhole prevention in the dry film production process are suppressed. It is preferable that long-term storage stability can be obtained, such as suppressing generation.

Therefore, an object of the present invention is to form a cured product with excellent electrical properties (HAST resistance), good long-term storage stability, and at least two-component composition capable of suppressing the occurrence of crawling and pinholes in the dry film manufacturing process. It is to provide a photocurable thermosetting resin composition.

Another object of the present invention is a dry film and cured product having excellent properties as described above obtained by using such an alkali developable solder resist composition, and a print formed by forming a cured film such as a solder resist by the dry film or cured product. It is to provide a wiring board.

As a result of intensive examination by the present inventors, the above problems are (A) epoxy resin, (B) carboxyl group-containing resin, (C) photopolymerization initiator, (D) photosensitive monomer, (E) silica, (F) barium sulfate and containing As a photocurable thermosetting resin composition,

In order to obtain the photocurable thermosetting resin composition, it is composed of at least a two-component resin composition,

The (B) carboxyl group-containing resin, the (D) photosensitive monomer, and the (E) silica are contained in a resin composition different from the (A) epoxy resin, the (F) barium sulfate, and the (C) photopolymerization initiator, ,

The resin composition containing the photopolymerization initiator (C) can be solved by a photocurable thermosetting resin composition composed of at least a two-component system, characterized in that it contains an organic solvent capable of dissolving the photopolymerization initiator (C). discovered, the present invention was completed.

Among them, a preferred embodiment of the present invention is (A) a photocurable thermosetting resin characterized in that it contains three types of epoxy resins, a semi-solid or solid epoxy resin at room temperature, a biphenyl type epoxy resin and a novolac type. It's about the composition.

A more preferable aspect of the present invention is that the composition containing the epoxy resin (A) has a viscosity of 4 dPa·s or less, and the photocurable thermosetting resin composition obtained by mixing the respective resin compositions has a viscosity of 4 dPa·s or less It relates to a photocurable thermosetting resin composition characterized by having.

A still more preferable aspect of the present invention is that the composition containing the (A) epoxy resin contains the (C) photopolymerization initiator and the organic solvent, and 3 parts by mass or more of the above with respect to 1 part by mass of the (C) photopolymerization initiator. It relates to a photocurable thermosetting resin composition characterized by containing an organic solvent.

Another aspect of the present invention relates to a dry film having a film thickness of 10 μm to 30 μm obtained by applying the photocurable thermosetting resin composition to a carrier film and drying it.

Another aspect of the present invention also relates to the photocurable thermosetting resin composition characterized in that it is for a solder resist material.

Another aspect of the present invention is a cured product obtained by curing a photocurable thermosetting resin composition, a cured product obtained by curing a resin layer of a dry film, and a cured product thereof. It's about electronic components.

According to the present invention, the cured product obtained by curing the photocurable thermosetting resin composition has excellent electrical properties (HAST resistance), and also has good long-term storage stability of each resin composition, and generation of crawling and pinholes in the dry film production process. It is possible to provide a photocurable thermosetting resin composition composed of at least a two-liquid system capable of suppressing.

Further, according to the present invention, a dry film and cured product having various properties as described above obtained by using such a photocurable thermosetting resin composition, and a printed wiring board formed by forming a cured film such as a solder resist by the dry film or cured product, etc. of electronic components can be provided.

The photocurable thermosetting resin composition of the present invention is preferably composed of at least a two-component resin composition. For example, a two-component system in which one resin composition is used as the main composition and the other resin composition is used as the curing agent composition is exemplified. In this case, for example, as the main composition, (B) a carboxyl group-containing resin, (D) a photosensitive monomer, (E) silica, and optionally an organic solvent, and as a curing agent composition, (A) epoxy It is preferable to set it as the thing of the composition containing the resin, (C) photoinitiator, (F) barium sulfate, and the organic solvent which can dissolve the said (C) photoinitiator.

Here, from the viewpoint of preventing a chemical reaction during the storage period, (A) epoxy resin, (B) carboxyl group-containing resin, (D) photosensitive monomer, and (C) photopolymerization initiator are each contained in separate compositions. desirable. In addition, (E) silica and (F) barium sulfate from the fact that separation of the liquid surface of each composition (color floating/color separation), so-called Bernard cell occurs, and the appearance of the liquid surface of each composition may be impaired. It is also preferable to divide and contain in different compositions.

In addition, when (B) the carboxyl group-containing resin and (C) the photopolymerization initiator are made into the same composition, although the detailed mechanism is unclear, appearance defects and coarse particles of the composition may occur, so (B) containing the carboxyl group-containing resin The composition is preferably contained in a composition different from (C) the photopolymerization initiator and the organic solvent for dissolving it.

Further, (A) the composition containing the epoxy resin has a viscosity of 4 dPa·s or less, and the photocurable thermosetting resin composition obtained by mixing the respective resin compositions has a viscosity of 0.1 dPa·s or more and 4 dPa·s or less , (A) Since precipitation of the epoxy resin can be suppressed, it is preferable. Moreover, if the viscosity of the composition containing (A) epoxy resin is 0.1 dPa*s or more, handling of a composition is easy and it is preferable.

Hereinafter, each component constituting the photocurable thermosetting resin composition of the present invention will be described.

[(A) Epoxy Resin]

(A) An epoxy resin functions as a thermosetting component in a photocurable thermosetting resin composition and forms a cured product.

As such (A) epoxy resin, a well-known and commonly used polyfunctional epoxy resin having at least two epoxy groups in one molecule can be used.

(A) The epoxy resin may be liquid or solid or semi-solid.

As a polyfunctional epoxy resin, it is bisphenol-A epoxy resin; brominated epoxy resins; novolak-type epoxy resins; bisphenol F-type epoxy resin; Hydrogenated bisphenol A type epoxy resin; glycidyl amine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; trihydroxy phenylmethane type epoxy resin; bixylenol type or biphenol type epoxy resins or mixtures thereof; bisphenol S type epoxy resin; bisphenol A novolac type epoxy resin; tetraphenylolethane type epoxy resin; heterocyclic epoxy resins; diglycidyl phthalate resin; tetraglycidylxylenoylethane resin; naphthalene group-containing epoxy resins; Epoxy resins having a dicyclopentadiene skeleton; glycidyl methacrylate copolymerization type epoxy resin; copolymerization epoxy resins of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives; A CTBN-modified epoxy resin, an epoxy resin having an isocyanuric ring, and the like are preferably exemplified, but of course it is not limited thereto.

These epoxy resins can be used singly or in combination of two or more.

As the epoxy resin, it is preferable to use a novolak-type epoxy resin with respect to a semi-solid or solid epoxy resin or biphenyl-type epoxy resin at room temperature. By using these epoxy resins together, it is possible to suppress the generation of crawling and pinholes at the time of dry film formation. Further, as the solid epoxy resin, an epoxy resin having a dicyclopentadiene skeleton is excellent in electrical properties because of its low water absorption, and is particularly preferred. With respect to the semi-solid or solid epoxy resin or biphenyl type epoxy resin at room temperature, the mixing ratio of the novolac type epoxy resin is the semi-solid or solid epoxy resin at room temperature:biphenyl type epoxy resin:novolak type epoxy resin=1 :1:1.5 is preferable, and 1:1:2 is more preferable.

(A) As for the "solid or semi-solid epoxy resin at room temperature" in the component, a known and commonly used one can be used. For example, as a solid epoxy resin at room temperature, bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. jER1001), bisphenol F type epoxy resin (Mitsubishi Chemical Co., Ltd. product jER4004P), naphthalene type epoxy resin (DIC (Co., Ltd.) ) HP-4700), polyfunctional solid epoxy resin containing naphthalene skeleton (NC-7000 manufactured by Nippon Kayaku Co., Ltd.), trisphenol epoxy resin (EPPN-502H manufactured by Nippon Kayaku Co., Ltd.), dicyclopentadiene skeleton Polyfunctional solid epoxy resin containing (Epiclon HP-7200 manufactured by DIC Corporation), phosphorus-containing epoxy resin (TX0712 manufactured by Nippon Steel & Chemical Co., Ltd.), tris(2,3-epoxypropyl) isocyanurate (Nissan Chemical Industry Co., Ltd. TEPIC), as a semi-solid epoxy resin at room temperature, bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. jER834), naphthalene type epoxy resin (DIC Co., Ltd. HP-4032) etc. can be mentioned.

Here, in the present invention, solid or semi-solid at room temperature means that it is solid or semi-solid at 15 ° C. Solid or semi-solid determination can be made in accordance with Annex 2 "Methods for Confirmation of Liquid Level" of the Ordinance on Testing and Characteristics of Dangerous Substances (Autonomous Ordinance No. 1 in 1989).

As the biphenyl type epoxy resin in the component (A), a known and commonly used polyfunctional epoxy resin having a biphenyl skeleton can be used. For example, biphenyl backbone-containing multifunctional solid epoxy resins (Nippon Kayaku Co., Ltd. product NC-3000H, NC-3000), biphenyl type epoxy resins (Mitsubishi Chemical Co., Ltd. product YX-4000, YL-6121HA) etc. can be mentioned.

As the novolak-type epoxy resin in component (A), cresol novolac-type epoxy resin (Epiclon N-690 manufactured by DIC Corporation), phenol novolak-type epoxy resin (Epiclon N-770 manufactured by DIC Corporation) , jER152) manufactured by Mitsubishi Chemical Corporation, and the like.

As described above, the content of the (A) epoxy resin is preferably in the range of about 30 to 60 parts by mass, and more preferably in the range of 35 to 45 parts by mass, based on 100 parts by mass of the following (B) carboxyl group-containing resin.

[(B) Carboxyl group-containing resin]

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

As a specific example of carboxyl group-containing resin which does not have an ethylenically unsaturated group, the following compounds (any of an oligomer and a polymer may be sufficient) are mentioned.

(1) Dialcohol compounds, polycarbonate polyols and polycarbonates containing diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, and carboxyl groups such as dimethylolpropionic acid and dimethylolbutanoic acid. Carboxyl group-containing urethane resin by polyaddition of diol compounds such as ether polyols, polyester polyols, polyolefin polyols, bisphenol A alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups .

(2) A carboxyl group-containing urethane resin by polyaddition reaction between diisocyanate and a carboxyl group-containing dialcohol compound.

(3) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, or isobutylene.

(4) A dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid is reacted with a bifunctional epoxy resin or a bifunctional oxetane resin, and hydroxyl groups generated by reacting phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. A polyester resin containing a carboxyl group to which a dibasic acid anhydride is added.

(5) A carboxyl group-containing resin obtained by ring-opening an epoxy resin or oxetane resin and reacting a polybasic acid anhydride with a produced hydroxyl group.

(6) A compound having a plurality of phenolic hydroxyl groups in one molecule, that is, a polyphenol compound obtained by reacting a polybasic acid anhydride with a reaction product such as a polyalcohol resin obtained by reacting a polyphenol compound with an alkylene oxide such as ethylene oxide or propylene oxide. Carboxyl group-containing resin.

Moreover, as a specific example of carboxyl group-containing resin which has an ethylenically unsaturated group, the following compounds (any of an oligomer and a polymer may be sufficient) are mentioned. In addition, it is preferable that the ethylenically unsaturated bond in the carboxyl group-containing resin is derived from acrylic acid or methacrylic acid or derivatives thereof.

(7) Dialcohol compounds containing diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and carboxyl groups such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate-based polyols, and polycarbonates. Carboxyl group by polyaddition reaction of diol compounds such as ether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A alkylene oxide adduct diol, compound having phenolic hydroxyl group and alcoholic hydroxyl group Contains photosensitive urethane resin.

(8) Bifunctional epoxy resins such as diisocyanate, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenol type epoxy resin A carboxyl group-containing photosensitive urethane resin by a polyaddition reaction between a (meth)acrylate or a partially modified acid anhydride thereof and a carboxyl group-containing dialcohol compound.

(9) During the synthesis of the resin of (7) or (8) described above, a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule such as hydroxyalkyl (meth)acrylate is added, (meth)acrylic carboxyl group-containing photosensitive urethane resin.

(10) During the synthesis of the resin of (8) or (9) described above, an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, etc., contains one isocyanate group and one or more (meth)acryloyl groups in the molecule. A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having terminal (meth)acrylation.

(11) A carboxyl group-containing photosensitive resin obtained by reacting (meth)acrylic acid with a bifunctional or more polyfunctional (solid) epoxy resin to add a dibasic acid anhydride to a hydroxyl group present in the side chain.

(12) Carboxyl group-containing photosensitive resin obtained by reacting (meth)acrylic acid with a multifunctional epoxy resin in which the hydroxyl group of a bifunctional (solid) epoxy resin is further epoxidized with epichlorohydrin, and a dibasic acid anhydride is added to the hydroxyl group generated.

(13) dibasic acids such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and the like to primary hydroxyl groups generated by reacting dicarboxylic acids such as adipic acid, phthalic acid, and hexahydrophthalic acid with bifunctional oxetane resin; Carboxyl group-containing polyester photosensitive resin to which an anhydride was added.

(14) Compounds having a plurality of phenolic hydroxyl groups in one molecule, that is, polyphenol compounds, are reacted with alkylene oxides such as ethylene oxide and propylene oxide to reaction products such as polyalcohol resins, such as (meth)acrylic acid A carboxyl group-containing photosensitive resin obtained by reacting an unsaturated group-containing monocarboxylic acid and further reacting a polybasic acid anhydride with a reaction product obtained.

(15) A 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 or propylene carbonate is reacted with a monocarboxylic acid containing an unsaturated group, and a polybasic acid anhydride is added to the reaction product obtained Carboxyl group-containing photosensitive resin obtained by making it react.

(16) A carboxyl group-containing photosensitive resin formed by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the above-mentioned resins (3) and (7) to (15).

These (B) carboxyl group-containing resin can also use things other than what was demonstrated as (7)-(16), and may be used individually by 1 type, or may mix and use multiple types. Among carboxyl group-containing resins, resins having an aromatic ring are particularly preferable because they have excellent resolution.

Since the above-mentioned (B) carboxyl group-containing resin has a large number of carboxyl groups in the side chain of the backbone polymer regardless of photosensitivity or non-photosensitivity, development with a dilute alkali aqueous solution is possible.

Moreover, (B) The range of 40-200 mgKOH/g is suitable for the acid value of carboxyl group-containing resin, More preferably, it is the range of 45-120 mgKOH/g. When the acid value of the carboxyl group-containing resin is within this range, alkali development is facilitated, dissolution of the exposed area by the developer is suppressed, lines do not become thinner than necessary, and normal patterns without dissolution and peeling by the developer can be drawn. It happens.

The mass average molecular weight of the above-mentioned (B) carboxyl group-containing resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, and preferably 5,000 to 100,000. When the mass average molecular weight is within this range, the tack-free performance is excellent, the moisture resistance of the coating film after exposure is good, and the resolution, developability, and storage stability are excellent.

The content of the carboxyl group-containing resin (B) is preferably in the range of 30 to 70% by mass, preferably 45 to 60% by mass, in the main composition. When the compounding amount of the carboxyl group-containing resin is within this range, the strength of the cured coating film does not decrease, and neither thickening nor deterioration in workability occurs.

[Acryloyl group-containing resin]

The present invention may further contain an acryloyl group-containing resin as an acrylate-based resin. The acryloyl group-containing resin of the present invention is a phenolic compound having two or more phenolic hydroxyl groups in a molecule having a structure of the following general formula (I) obtained by a condensation reaction between a polymethylol of bisphenol A or bisphenol F and phenols. (a), namely, by using a novolac-type phenolic resin having a specific structure, the drying property of the ink composition before curing is improved, and by converting some or all of the phenolic hydroxyl groups of this resin into oxyalkyl groups having alcoholic hydroxyl groups, flexibility is achieved. is added, and by adding acrylic acid and/or methacrylic acid (c) to the terminal hydroxyl group of the resulting oxyalkyl group, since the α,β-ethylenically unsaturated group is imparted to the terminal of the side chain, the reactivity is improved. , a high level of balance between heat resistance and toughness, excellent hardness and flexibility, as well as excellent water resistance, chemical resistance, etc., can be obtained.

(Wherein, R ₁ is -C(CH ₃ ) ₂ - or -CH ₂ -, R ₂ is a hydrocarbon group having 1 to 11 carbon atoms, a is an integer of 0 to 3, and n is an integer of 1 to 2 Represents, m represents an integer from 1 to 10.)

The phenolic compound (a) having two or more phenolic hydroxyl groups in a molecule having the structure of the general formula (I) is obtained by subjecting a polymethylol of bisphenol A or bisphenol F to a condensation reaction of phenols in the presence of an acidic catalyst.

As the phenols, alkylphenols such as phenol, various types of cresols, various types of xylenols, and naphthols can be used, and o-cresol and 2,6-xylenol are preferably used. Moreover, you may mix and use these.

The addition ratio of the compound (b) having a cyclic ether group such as an alkylene oxide or a cyclic carbonate to the phenolic compound (a) is 0.5 mol per equivalent of phenolic hydroxyl group of the phenolic compound (a), preferably 0.8 to 3.0. Mall is good. In the case of the range of 0.5 to 5.0 mol, in the obtained acryloyl group-containing photosensitive resin, photocurability and drying properties are excellent.

The content of such acryloyl group-containing resin is preferably in the range of 5 to 20% by mass, preferably 8 to 15% by mass, in the main composition.

[(C) Photopolymerization Initiator]

(C) Examples of the photopolymerization initiator include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, and bis-(2). ,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, Bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2 bisacylphosphine oxides such as ,4,6-trimethylbenzoyl)-phenylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, p monoacylphosphine oxides such as valoylphenylphosphinic acid isopropyl ester and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 1-Hydroxy-cyclohexylphenylketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1 -{4-[4-(2-Hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan- hydroxyacetophenones such as 1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2- acetophenones such as (dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-morpholinyl)phenyl]-1-butanone and N,N-dimethylaminoacetophenone; Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-di Thioxanthone, such as isopropyl thioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carb oxime esters such as bazol-3-yl] -,1-(O-acetyl oxime); Bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)- titanocenes such as bis[2,6-difluoro-3-(2-(1-phyll-1-yl)ethyl)phenyl]titanium; Phenyl disulfide 2-nitrofluorene, butyloin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. are mentioned. A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

(C) It is preferable that content of a photoinitiator is 5-15 mass parts with respect to 100 mass parts of (B) carboxyl group-containing resin. In the case of 5 parts by mass or more, surface hardenability becomes good, and in the case of 15 parts by mass or less, halation hardly occurs and good resolution is obtained.

[(D) photosensitive monomer]

The photocurable thermosetting resin composition capable of forming the cured product of the present invention may contain a known and commonly used photosensitive monomer. (D) The photosensitive monomer may be, for example, a compound having one or more ethylenically unsaturated groups in the molecule. Such (D) photosensitive monomer helps photocuring of (B) carboxyl group-containing resin by active energy ray irradiation (when an ethylenically unsaturated group is contained), and cures a photocurable thermosetting resin composition.

The (D) photosensitive monomer preferably used in the present invention is, for example, α-(allyloxymethyl)methyl acrylate, or 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1, diacrylates of diols such as 9-nonanediol diacrylate and 1,10-decanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate rate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, at least one of ethylene oxide and propylene oxide in neopentyl glycol Diacrylates of diols obtained by addition of species, diacrylates of glycols such as caprolactone-modified hydroxypivalate neopentyl glycol diacrylate, diacrylates of EO adducts of bisphenol A, and diacrylates of PO adducts of bisphenol A Diacrylates having a cyclic structure such as tricyclodecanedimethanol diacrylate, hydrogenated dicyclopentadienyl diacrylate, and cyclohexyl diacrylate, or bifunctional such as methacrylate monomers corresponding to these ( meth)acrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolmethane triacrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane triacrylate, epichlorohydrin Modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, tetramethylolmethane tetraacrylate, ethylene oxide modified phosphoric acid triacrylate, epichlorohydrin modified glycerol triacrylate, di Pentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, or polyfunctional acrylates represented by these silsesquioxane modified products, etc., or methacrylate monomers and trifunctional methacrylates corresponding to these esters, polyfunctional (meth)acrylates such as ε-caprolactone-modified tris(acryloxyethyl)isocyanurate, or combinations of two or more thereof; and the like.

The content of the photosensitive monomer (D) is preferably in the range of 10 to 27 parts by mass, and more preferably in the range of 15 to 20 parts by mass with respect to the total of 100 parts by mass (solid content) of the carboxyl group-containing resin (B).

(D) When the content of the photosensitive monomer is within this range, the photocurable thermosetting resin composition has sufficient photocurability, better patterning during development, and better tackiness (dry to touch).

[(E) Silica]

In the present invention, silica (E) is preferably contained in the main composition in the case of a two-component system as a filler. (E) Silica is preferably used in the present invention because of its low hygroscopicity and low volume expansibility.

(E) Silica may be either amorphous or crystalline, or a mixture thereof, but an amorphous one is preferable.

In the present invention, from the viewpoint of ease of handling, such as maintaining the degree of dispersion, the (E) silica is usually preferably used as a slurry dispersed in a solvent.

[(F) Barium Sulfate]

In the present invention, barium sulfate (F) also acts as a filler, similarly to silica (E), but apart from silica (E), it is preferably contained in the curing agent composition and not in the main composition. This is because there is a possibility of damaging the appearance of the coating film of the composition obtained from the composition after mixing, such as generation of Bernard cells. In the present invention, from the viewpoint of ease of handling, such as maintaining the degree of dispersion, the (F) barium sulfate is usually preferably used as a slurry dispersed in a solvent.

As the silica (E) and the barium sulfate (F), those subjected to surface treatment are preferable, and it is more preferable that a surface treatment capable of introducing a curable reactive group is performed on their surfaces.

Here, a curable reactive group refers to (A) an epoxy resin or the like and (B) a group that undergoes a curing reaction with a carboxyl group-containing resin, and may be a photocurable reactive group or a thermosetting reactive group. Examples of photocurable reactive groups include methacrylic groups, acrylic groups, vinyl groups and styryl groups, and examples of thermosetting reactive groups include epoxy groups, amino groups, hydroxyl groups, carboxyl groups, isocyanate groups, imino groups, oxetanyl groups, mercapto groups, and methoxy groups. A methyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, an oxazoline group, etc. are mentioned.

The method of introducing a curable reactive group into the surfaces of (E) silica and (F) barium sulfate is not particularly limited, and may be introduced using a known and usual method, and a surface treatment agent having a curable reactive group, for example, a curable reactive group is used. What is necessary is just to process the surface of an inorganic filler with the coupling agent etc. which it has as a device. As a coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, etc. can be used. In addition, as a surface-treated inorganic filler which does not have a curable reactive group, the silica-alumina surface treatment, a titanate-type coupling agent process, an aluminate-type coupling agent process, the inorganic filler etc. which were organically treated are mentioned, for example.

(E) As an average particle diameter (D50) of a silica slurry, it is 2000 nm or less, and it is more preferable that it is 1200 nm or less. In addition, the lower limit is preferably 0.1 nm or more as an average particle diameter (D50).

(F) The average particle diameter (D50) of the barium sulfate slurry is 1000 nm or less, more preferably 500 nm or less. In addition, the lower limit is preferably 0.1 nm or more as an average particle diameter (D50).

As the average particle diameters of (E) silica and (F) barium sulfate are smaller, irregular reflection during light irradiation can be suppressed, and fine processing of the cured product pattern can be facilitated.

The average particle size (D50) can be determined by a laser diffraction type particle size distribution measuring device and a measuring device using a dynamic light scattering method. As a measuring device by the laser diffraction method, Microtrac MT3300EXII manufactured by Microtrac Bell, Inc., and Nanotrac Wave II UT151 manufactured by Microtrac Bell, Inc. are mentioned as a measuring device by the dynamic light scattering method.

The content of (E) silica and (F) barium sulfate is the photocurable property of the present invention from the viewpoint of being able to match and impart characteristics required for solder resists such as suppression of heat shielding, high resolution, and good crack resistance. 15 mass % - 30 mass % are more preferable respectively with respect to the total amount of non-volatile components of a thermosetting resin composition.

[organic solvent]

In the present invention, an organic solvent may be used to prepare a photocurable thermosetting resin composition or to adjust its viscosity, or to prepare (E) a silica slurry or (F) a barium sulfate slurry.

Examples of such organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons, such as toluene, xylene, and tetramethylbenzene; Cellosolve, Methyl Cellosolve, Butyl Cellosolve, Carbitol, Methyl Carbitol, Butyl Carbitol, Propylene Glycol Monomethyl Ether, Dipropylene Glycol Monomethyl Ether (DPM), Dipropylene Glycol Diethyl Ether, Tripropylene Glycol glycol ethers such as monomethyl ether; esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; Petroleum-based solvents, such as petroleum ether, petroleum naphtha, and solvent naphtha, etc. can be used.

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

The content of the organic solvent is preferably in the range of 5% by mass to 25% by mass with respect to the main composition of the photocurable thermosetting resin composition of the present invention. In addition, the content of this organic solvent includes (E) the organic solvent in the silica slurry.

Regarding the curing agent composition, it is an organic solvent capable of dissolving the (C) photopolymerization initiator to be incorporated into the composition, and preferably contains 3 parts by mass or more of the organic solvent per 1 part by mass of the photopolymerization initiator (C). (C) The organic solvent capable of dissolving the photopolymerization initiator means an organic solvent in which "○: crystals of the photopolymerization initiator are not visible visually" (see Table 1) as a result of the "confirmation test of the solubility of the photopolymerization initiator" described later. . By selecting and using such an organic solvent, crystals of the photopolymerization initiator (C) do not form, so generation of coarse particles can be suppressed.

Among the organic solvents listed in Table 1, since PMA and CA are excellent in the coating properties of the photocurable thermosetting resin composition after mixing and the dryness to the touch after coating, it is more preferable to use PMA alone or a mixed solvent of PMA and CA. .

In addition, the upper limit of the content of the organic solvent can be appropriately adjusted according to the maximum dissolved amount of the photopolymerization initiator (C) (see Table 2 below). Photoinitiators other than Omnirad TPO H described in Tables 1-2 to 1-5 can also be appropriately adjusted in the same way.

[Other Ingredients]

In the photocurable thermosetting resin composition of the present invention, it is of course possible to incorporate further additives as other components as needed within a range not departing from the object of the present invention.

As such components, for example, coloring agents such as pigments and dyes, thermal polymerization inhibitors, ultraviolet absorbers, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial and antifungal agents, leveling agents, thickeners, adhesion imparting agents, thixotropic imparting agents, photoinitiation aids, sensitizers, photobase generators, thermoplastic resins, elastomers, organic fillers, fillers other than silica and barium sulfate, release agents, surface treatment agents, dispersants, dispersion aids, surface modifiers, stabilizers, phosphors, cellulose resins, etc. can be heard

The main composition and curing agent composition of the photocurable thermosetting resin composition of the present invention can be prepared by mixing and dispersing each of these components in predetermined amounts, for example, with a three roll mill or the like.

[Dry Film]

It is preferable to use the photocurable thermosetting resin composition of this invention, forming a dry film.

The dry film of this invention has a resin layer obtained by apply|coating and drying the photocurable thermosetting resin composition of this invention on a carrier film. When forming a dry film, first, in the case of a two-component system, the main composition and the curing agent composition are mixed well to obtain the photocurable thermosetting resin composition of the present invention, and then diluted with an organic solvent as it is or if necessary, and appropriate After adjusting the viscosity, it is applied to a uniform thickness on the carrier film by a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater or the like. After that, the resin layer can be formed by drying the applied composition at a temperature of usually 50 to 130°C for 1 to 30 minutes. The coating film thickness is not particularly limited, but is generally appropriately selected from the range of 10 to 150 µm, preferably 20 to 60 µm, as the film thickness after drying.

As the carrier film, a plastic film is used, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used. The thickness of the carrier film is not particularly limited, but is generally appropriately selected from the range of 10 to 150 µm.

After forming a resin layer containing the photocurable thermosetting resin composition of the present invention on a carrier film, a cover film that can be peeled off from the surface of the resin layer for the purpose of preventing dirt from adhering to the surface of the resin layer. It is preferable to laminate them. As a peelable cover film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, etc. can be used, for example. As a cover film, when peeling a cover film, what is necessary is just to be smaller than the adhesive force of a resin layer and a carrier film.

Further, in the present invention, a resin layer may be formed by applying and drying the photocurable thermosetting resin composition of the present invention on the cover film, and then a carrier film may be laminated on the surface. That is, when manufacturing a dry film in this invention, you may use any of a carrier film and a cover film as a film to which the curable composition of this invention is apply|coated.

Here, the photocurable thermosetting resin composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, an organic solvent, and applied on the substrate by dip coating method, flow coating method, roll coating method, bar coater method, screen After applying by a method such as a printing method or a curtain coating method, a tack-free resin layer may be formed by volatilizing and drying (pre-drying) the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. In addition, in the case of a dry film in which the composition is applied on a carrier film or cover film, dried, and wound as a film, the layer of the composition of the present invention is bonded on the substrate so that the layer of the composition of the present invention is in contact with the substrate by a laminator or the like, and then the carrier film is By peeling, a resin layer can be formed.

Examples of the base materials include printed wiring boards and flexible printed wiring boards formed with copper or the like in advance, as well as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven fabric epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, and fluororesin.・Materials such as copper-clad laminates for high-frequency circuits using polyethylene/polyphenylene ether, polyphenylene oxide/cyanate, etc., copper-clad laminates of all grades (FR-4, etc.), other metal substrates, polyimide films , PET film, polyethylene naphthalate (PEN) film, glass substrate, ceramic substrate, wafer plate and the like.

[cured material]

In order to form a cured product using the photocurable thermosetting resin composition of the present invention, the composition is applied on a substrate, and the resin layer obtained after volatilizing and drying the solvent is exposed (light irradiation) to the exposed portion ( light-irradiated portion) is hardened. Specifically, by a contact or non-contact method, exposure is selectively performed with an active energy ray through a photomask in which a pattern is formed, or direct pattern exposure is performed using a laser direct exposure machine, and the unexposed portion is exposed to an alkali aqueous solution (for example, 0.3 to 3% by mass of sodium carbonate aqueous solution), a resist pattern is formed. In addition, by heating and thermally curing (post-curing) at a temperature of about 100 to 180 ° C., a cured film (cured product) excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties can be formed.

Volatilization drying or thermal curing at the time of forming the cured product is, for example, a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, etc. A method of countercurrently contacting hot air and a method of spraying from a nozzle to a support) can be used.

In addition, the exposure machine used for the active energy ray irradiation may be an apparatus equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like, and irradiating ultraviolet rays in the range of 350 to 450 nm. A direct drawing device (for example, a laser direct imaging device that draws an image with a laser directly by CAD data from a computer) can also be used. As the lamp light source or laser light source of the weaving machine, the maximum wavelength should just exist in the range of 350-410 nm. The exposure amount for image formation varies depending on the film thickness and the like, but is generally within the range of 20 to 1000 mJ/cm 2 , preferably 20 to 800 mJ/cm 2 .

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

[Electronic parts]

In addition, the present invention can also provide an electronic component having the cured product.

By using the photocurable thermosetting resin composition of the present invention, an electronic component having high quality, durability and reliability is provided.

In the present invention, electronic components refer to components used in electronic circuits, and other active components such as printed wiring boards, transistors, light emitting diodes, and laser diodes, and passive components such as resistors, capacitors, inductors, and connectors are also included. .

Hereinafter, one aspect of the present invention is specifically shown by examples, but, of course, it is not the purpose to limit the scope of the invention relating to the claims of the present application.

In addition, "part" and "%" appearing shall be based on mass unless otherwise indicated.

Example

Test Example 1. Confirmation of solubility of photopolymerization initiator

Prior to experiments on each characteristic of the photocurable thermosetting resin composition of the present invention, in order to select a suitable organic solvent for the photopolymerization initiator, a test to confirm the solubility of 5 kinds of photopolymerization initiators in the organic solvent was conducted in advance. It was done as follows.

Initially, a test was conducted to confirm the general solubility of the five photopolymerization initiators in various organic solvents, and it was used as a standard for setting the amount of addition thereafter (Tables 1-1 to 1-5).

Then, a prescribed amount of four types of solvents was added to the prepared vial bottle, respectively, and a photopolymerization initiator (Omnirad TPO H) was further added to the vial bottle, followed by shaking by hand and stirring, followed by standing still for 5 minutes. Thereafter, the presence or absence of crystals of the photopolymerization initiator was visually confirmed, and when crystals were not confirmed, the photopolymerization initiator was further added, stirred by hand, and allowed to stand for 5 minutes. This operation is repeated until crystals are confirmed, and finally, when crystals are confirmed after standing for 5 minutes, the addition of the photopolymerization initiator is finished, and the addition amount before the crystals are confirmed is set to the maximum value of the photopolymerization initiator Omnirad TPO H. It was used as the added amount (Table 2).

The evaluation criteria are as follows.

○: Crystals of the photopolymerization initiator were not observed visually.

x: Crystals of the photopolymerization initiator were observed visually (not dissolved with time)

The results are shown in Tables 1-1 to 1-5 and Table 2 below.

[Table 1-1]

[Table 1-2]

[Table 1-3]

[Table 1-4]

[Table 1-5]

[Table 2]

*The photopolymerization initiator and organic solvent described in Tables 1-1 to 1-5 and Table 2 are as follows.

TPO: Acylphosphine oxide-based photopolymerization initiator (Omnirad TPO H manufactured by IGM Resins B.V.) (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide)

907: α-aminoacetophenone-based photopolymerization initiator (IGM Resins Omnirad 907) (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one)

379: Alkylphenone-based photopolymerization initiator (Omnirad 379EG manufactured by IGM Resins B.V.) (2- (dimethylamino) -2- (4-methylbenzyl) -1- (4-morpholino phenyl) butan-1one)

784: titanocene-based photopolymerization initiator (JMT-784 manufactured by Yueyang Jinmaotai Keji Co., Ltd.)

OXE02: Oxime ester photopolymerization initiator (BASF Japan Irgacure OXE02 (ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(o -acetyl oxime)

・PMA (Propylene Glycol Monomethyl Ether Acetate)

CA (Carbitol Acetate)

・GBL (γ-butyrolactone)

MEK (methyl ethyl ketone)

[Synthesis Example 1. Synthesis of Carboxyl Group-Containing Resin (B-1)]

In a flask equipped with a cooling tube and a stirrer, 456 parts of bisphenol A, 228 parts of water, and 649 parts of 37% formalin were added, the temperature was maintained below 40 ° C, 228 parts of 25% sodium hydroxide aqueous solution was added, and after the addition was completed, 50 It reacted at °C for 10 hours. After completion of the reaction, the mixture was cooled to 40°C and neutralized to pH 4 with a 37.5% aqueous phosphoric acid solution while maintaining the temperature below 40°C. After that, it was settled and the water layer was separated. After separation, 300 parts of methyl isobutyl ketone was added and uniformly dissolved, and then washed three times with 500 parts of distilled water, and water, solvent and the like were removed under reduced pressure at a temperature of 50°C or lower. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanol solution of the polymethylol compound. When a part of the obtained methanol solution of the polymethylol compound was dried at room temperature in a vacuum dryer, the solid content was 55.2%.

500 parts of the methanol solution of the obtained polymethylol compound and 440 parts of 2,6-xylenol were introduced and uniformly dissolved at 50°C. After uniformly dissolving, methanol was removed under reduced pressure at a temperature of 50°C or lower. After that, 8 parts of oxalic acid was added, and it reacted at 100 degreeC for 10 hours. After completion of the reaction, distillate was removed at 180°C under reduced pressure of 50 mmHg to obtain 550 parts of novolak resin A. In addition, in an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device, 130 parts of the novolac resin A, 2.6 parts of a 50% sodium hydroxide aqueous solution, toluene / methyl isobutyl ketone (mass ratio = 2/ 1) 100 parts were introduced, the inside of the system was substituted with nitrogen while stirring, then the temperature was raised by heating, and 45 parts of ethylene oxide was gradually introduced and reacted at 150°C and 8 kg/cm 2 . The reaction was continued for about 4 hours until the gauge pressure reached 0.0 kg/cm 2 , then cooled to room temperature. To this reaction solution, 3.3 parts of a 36% hydrochloric acid aqueous solution was added and mixed to neutralize sodium hydroxide. This neutralization reaction product was diluted with toluene, washed with water three times, and solvent removed in an evaporator to obtain an ethylene oxide adduct of novolak resin A having a hydroxyl value of 175 g/eq. This was that an average of 1 mol of ethylene oxide was added per 1 equivalent of phenolic hydroxyl group.

175 parts of the ethylene oxide adduct of the novolac resin A thus obtained, 50 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 part of hydroquinone monomethyl ether, and 130 parts of toluene were introduced into a reactor equipped with a stirrer, a thermometer and an air intake pipe The mixture was stirred while blowing air, and the temperature was raised to 115°C, and the reaction was allowed to react for further 4 hours while distilling off the water produced by the reaction as an azeotropic mixture with toluene, and then cooled to room temperature. The obtained reaction solution was washed with water using a 5% NaCl aqueous solution, and after removing toluene by distillation under reduced pressure, diethylene glycol monoethyl ether acetate was added to obtain an acrylate resin solution having a solid content of 68%.

Subsequently, 312 parts of the obtained acrylate resin solution, 0.1 part of hydroquinone monomethyl ether, and 0.3 part of triphenylphosphine were added to a four-necked flask equipped with a stirrer and a reflux condenser, and the mixture was heated to 110°C and tetrahydrogenated. 45 parts of phthalic anhydride was added, it was made to react for 4 hours, and it took out after cooling. The carboxyl group-containing resin (B-1) obtained in this way was 72% of non-volatile content and 65 mgKOH/g of solid content acid value.

[Synthesis Example 2. Synthesis of Carboxyl Group-Containing Resin (B-2)]

In an autoclave equipped with a thermometer, a nitrogen introducing device, an alkylene oxide introducing device, and a stirring device, 119.4 parts of cresol novolac resin (Shonol CRG-951 manufactured by Aika Kogyo, OH equivalent: 119.4), 1.19 parts of potassium hydroxide, and 119.4 parts of toluene were introduced. While stirring, the inside of the system was purged with nitrogen, and the temperature was raised by heating. Then, 63.8 parts of propylene oxide was gradually added dropwise and reacted at 125 to 132°C and 0 to 4.8 kg/cm 2 for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and potassium hydroxide was neutralized by adding and mixing 1.56 parts of 89% phosphoric acid to the reaction solution. A propylene oxide reaction solution of cresol resin was obtained. This was obtained by adding an average of 1.08 mol of propylene oxide per 1 equivalent of phenolic hydroxyl group.

293.0 parts of the obtained propylene oxide reaction solution of the novolak-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone, and 252.9 parts of toluene were introduced into a reactor equipped with a stirrer, a thermometer and an air blowing pipe, and air was blown into the reactor. It was made to react at 110 degreeC for 12 hours, blowing and stirring at the speed|rate of 10 ml/min. The water produced|generated by reaction was an azeotropic mixture with toluene, and 12.6 parts of water distilled out. Then, it cooled to room temperature, and neutralized the obtained reaction solution with 35.35 parts of 15% sodium hydroxide aqueous solution, and then washed with water. Thereafter, toluene was distilled off while replacing toluene with 118.1 parts of diethylene glycol monoethyl ether acetate in an evaporator to obtain a novolak-type acrylate resin solution.

Then, 332.5 parts of the obtained novolak-type acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air blowing tube, air was blown in at a rate of 10 ml/min, and while stirring, 60.8 parts of hydrophthalic anhydride were added gradually, it was made to react at 95-101 degreeC for 6 hours, and it took out after cooling. In this way, a carboxyl group-containing resin (B-2) having a solid content of 65% and an acid value of 87.7 mgKOH/g of the solid content was obtained.

[Synthesis Example 3. Synthesis of Acryloyl Group-Containing Resin]

In a flask equipped with a cooling tube and a stirrer, 456 parts of bisphenol A, 228 parts of water, and 649 parts of 37% formalin were added, the temperature was maintained below 40 ° C, 228 parts of 25% sodium hydroxide aqueous solution was added, and after the addition was completed, 50 It reacted at °C for 10 hours. After completion of the reaction, the mixture was cooled to 40°C and neutralized to pH 4 with a 37.5% aqueous phosphoric acid solution while maintaining the temperature below 40°C. After that, it was settled and the water layer was separated. After separation, 300 parts of methyl isobutyl ketone was added and uniformly dissolved, and then washed three times with 500 parts of distilled water, and water, solvent, etc. were removed under reduced pressure at a temperature of 50°C or lower. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanol solution of the polymethylol compound. When a part of the obtained methanol solution of the polymethylol compound was dried at room temperature in a vacuum dryer, the solid content was 55.2%.

500 parts of the methanol solution of the obtained polymethylol compound and 440 parts of 2,6-xylenol were introduced and uniformly dissolved at 50°C. After uniformly dissolving, methanol was removed under reduced pressure at a temperature of 50°C or lower. After that, 8 parts of oxalic acid were added and reacted at 100°C for 10 hours. After completion of the reaction, distillate was removed at 180°C under reduced pressure of 50 mmHg to obtain 550 parts of novolak resin A. In addition, in an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device, 130 parts of the novolac resin A, 2.6 parts of a 50% sodium hydroxide aqueous solution, toluene / methyl isobutyl ketone (mass ratio = 2/ 1) 100 parts were introduced, the inside of the system was substituted with nitrogen while stirring, then the temperature was raised by heating, and 45 parts of ethylene oxide was gradually introduced and reacted at 150°C and 8 kg/cm 2 . The reaction was continued for about 4 hours until the gauge pressure reached 0.0 kg/cm 2 , then cooled to room temperature. To this reaction solution, 3.3 parts of a 36% hydrochloric acid aqueous solution was added and mixed to neutralize sodium hydroxide. This neutralization reaction product was diluted with toluene, washed with water three times, and solvent removed in an evaporator to obtain an ethylene oxide adduct of novolak resin A having a hydroxyl value of 175 g/eq. This was that an average of 1 mol of ethylene oxide was added per 1 equivalent of phenolic hydroxyl group.

175 parts of ethylene oxide adduct of novolac resin A thus obtained, 75 parts of methacrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 part of hydroquinone monomethyl ether, 130 parts of toluene A reactor equipped with a stirrer, a thermometer, and an air blowing pipe , stirred while blowing in air, heated to 115°C, and reacted for 4 hours while distilling off the water produced by the reaction as an azeotropic mixture with toluene, and then cooled to room temperature. The obtained reaction solution was washed with water using a 5% NaCl aqueous solution, and after removing toluene by distillation under reduced pressure, diethylene glycol monoethyl ether acetate was added to obtain an acryloyl group-containing resin solution having a solid content of 68%.

(E) preparation of silica slurry

700 g of spherical silica (SO-E2 manufactured by Admatech), 295 g of propylene glycol monomethyl ether acetate (PMA) as a solvent, and 5 g of a wet dispersant were mixed and stirred, and dispersed using 0.5 μm zirconia beads in a bead mill. This was repeated 3 times and filtered with a 3 μm filter to prepare a (E) silica slurry. The average particle diameter (D50) of the obtained silica slurry was 1200 nm or less.

(F) preparation of barium sulfate slurry

700 g of barium sulfate (B-30 manufactured by Sakai Kagaku Kogyo Co., Ltd.), 295 g of diethylene glycol monoethyl ether acetate (carbitol acetate) as a solvent, and 5 g of a wet dispersing agent were mixed and stirred, and a dispersion treatment was performed in a bead mill in the same manner as above. This was repeated three times and filtered with a 3 μm filter to prepare a barium sulfate slurry (F). The average particle diameter (D50) of the obtained barium sulfate slurry was 500 nm or less.

[Examples 1 to 5 and Comparative Examples 1 to 3]

As shown in Tables 3 and 4 below, each component was premixed in each compounding amount with a stirrer, and then kneaded with a three-roll mill, and the photocurable thermosetting resin composition of Examples 1 to 5 and Comparative Examples 1 to 3 (the main subject A two-liquid system comprising the composition and the curing agent composition) were prepared, respectively.

[Table 3]

[Table 4]

^*1 According to Synthesis Example 1

^*2 Based on Synthesis Example 2

^*3 According to Synthesis Example 3

^*4 CIPigment red 149

^*5 CIPigment yellow 147

^*6 Copper phthalocyanine blue:

^*7 Carbon black: MA-100 (Mitsubishi Chemical Co., Ltd.)

^*8 Melamine

^*9 BYK-350 (made by Big Chemie Japan)

^*10 DPHA: dipentaerythritol hexaacrylate (hexafunctional acrylic monomer, manufactured by Nippon Kayaku Co., Ltd.)

^*11 Laromer LR8863: EO modified trimethylolpropane triacrylate (manufactured by BASF Japan)

^*12 (E) silica slurry

^*13 PMA (Propylene Glycol Monomethyl Ether Acetate)

^*14 (F) Barium sulfate slurry

^*15 CA (Carbitol Acetate)

^*16 Omnirad TPO H: Acylphosphine oxide-based photopolymerization initiator (manufactured by IGM Resins B.V.)

^*17 JMT784: titanocene-based photopolymerization initiator (manufactured by Yueyang Jinmaotai Keji Co., Ltd.)

^*18 Quinopower QS-30: naphthoquinone polymerization inhibitor (manufactured by Kawasaki Kasei Kogyo Co., Ltd.)

^*19 PMA (Propylene Glycol Monomethyl Ether Acetate)

^*20 GBL (γ-butyrolactone)

^*21 MEK (methyl ethyl ketone)

^*22 dicyclopentadiene type epoxy resin (HP-7200L; manufactured by DIC)

^*23 BisA type epoxy resin (jER834; manufactured by Mitsubishi Chemical Corporation)

^*24 Biphenyl type epoxy resin

^*25 novolak epoxy resin

The main composition and curing agent composition of Examples 1 to 5 and Comparative Examples 1 to 3 and the photocurable thermosetting resin composition obtained by mixing them were tested as follows.

<Dispersion (initial), initial viscosity>

The viscosity of each of the main compositions of Examples 1 to 5 and Comparative Examples 1 to 3, the curing agent composition, and the photocurable thermosetting resin composition obtained by mixing the main composition and the curing agent composition well was measured by a cone plate type viscometer (model number: TVE-33H). , manufactured by Tokyo Keiki Co., Ltd.), the measurement was performed at a measurement temperature of 25°C and a cone rotation speed of 5 rpm/min, and the numerical value was used as the initial viscosity. The degree of dispersion was measured by particle size measurement using a grind meter (manufactured by Yasuda Seiki Seisakusho), and the numerical value was used as the degree of dispersion (initial stage).

The results are summarized in Table 5 below.

[Table 5]

<Dispersion (over time)>

For each of the main composition and curing agent composition of Examples 1 to 5 and Comparative Examples 1 to 3, 5 days, 10 days, and 15 days after preparation when stored at 20 ° C and 5 ° C , The degree of dispersion after 20 days and 30 days was measured by particle size measurement using a grind meter (manufactured by Yasuda Seiki Seisakusho), and the numerical value was used as the degree of dispersion (with time).

The evaluation criteria are as follows.

<10㎛ : ○

<12.5㎛ : △

<20㎛: ×

The results are summarized in Table 6 below.

[Table 6]

<Appearance of composition>

For each of the main compositions and curing agent compositions of Examples 1 to 5 and Comparative Examples 1 to 3, 5 days, 10 days, 15 days, 20 days and 30 days after preparation when stored at 20 ° C. The surface of each composition in the later was visually confirmed.

The evaluation criteria are as follows.

No surface separation: ○

With separation of the surface: ×

The results are summarized in Table 7 below.

[Table 7]

<Appearance of dry film>

Photocurability obtained by storing the main compositions and curing agent compositions of Examples 1 to 5 and Comparative Examples 1 to 3 at 20° C., and mixing them after 5 days, 10 days, 15 days, 20 days, and 30 days, respectively. With respect to the thermosetting resin composition, the viscosity was adjusted to 4d·Ps by adding a diluting solvent. Then, the photocurable thermosetting resin composition after dilution was applied to a PET film using an applicator so that the film thickness after drying was 15 μm and 30 μm, respectively, and dried in a hot air circulation drying furnace for 30 minutes. Thereafter, the surface (30 cm × 30 cm) of the obtained coating film was observed with an optical microscope x 20, and the number of occurrences of crawling and pinholes was confirmed.

The evaluation criteria are as follows.

0 : ○

1 or more and 5 or less: △

More than 5 and up to 10: ×

The results are summarized in Table 8 below.

[Table 8]

<Electrical Characteristics>

From the photocurable thermosetting resin composition obtained by mixing the main composition and the curing agent composition of Examples 1 to 5 and Comparative Examples 1 to 3, using a comb-shaped electrode pattern with line/space = 20/20 μm instead of a copper foil substrate, dry dry each film was obtained. A vacuum heating laminate was performed on the obtained dry film, a bias voltage of DC 10V was applied, and the time until the insulation resistance value became 10 to the 4th power Ω or less at 130°C/85% was measured. In addition, the average time using 5 pieces of the number of measurements was calculated.

The evaluation criteria are as follows.

Connection time 200 hours or more and 250 hours or less: ○

Access time 150 hours or more and less than 200 hours: ×

The results are summarized in Table 9 below.

[Table 9]

From the results shown in the table above, it can be seen that the photocurable thermosetting resin composition of the present invention has excellent electrical properties. It can be seen that both the main composition and the curing agent composition of the present invention had a particle size measurement result of <10 μm using a grind meter from the initial stage to 30 days after storage, no generation of coarse particles, and excellent dispersibility and storage stability. .

In addition, regarding the appearance of the composition, it was found that both the main composition and the curing agent composition did not have problems such as surface separation, and had excellent storage stability even after 30 days of storage.

In addition, the photocurable thermosetting resin composition of the present invention does not generate crawling and pinholes during dry film formation up to 30 days after storage, and is excellent in storage stability also in this respect.

On the other hand, the main composition of Comparative Example 1 contains (B) a carboxyl group-containing resin and (C) a photopolymerization initiator, and since it contains both, the detailed mechanism is unknown, but compared with each Example, the dispersion (with time) ), it can be seen that the stability of the composition over time is poor. In addition, since the curing agent composition of Comparative Example 1 contains (E) silica and (F) barium sulfate, separation of the liquid surface (color lifting/color separation), so-called Bernard cells, occurs, and the liquid surface of the composition It can be seen that the appearance is damaged and the stability over time is poor.

The main composition of Comparative Example 2 contains (B) a carboxyl group-containing resin and (C) a photopolymerization initiator, and since it contains both, the detailed mechanism is unknown, but compared with each Example, the degree of dispersion (with time), It is inferior in the apparent aging stability of the composition, and since it also contains (E) silica and (F) barium sulfate, a so-called Bernard cell occurs, and compared with each Example, the dispersity (with time), the apparent aging stability of the composition falling can be seen.

The main composition of Comparative Example 3 does not contain (E) silica, and the curing agent composition does not contain (E) silica and only contains (F) barium sulfate, that is, both components are not used together in one composition. Further, in the main composition, since (B) the carboxyl group-containing resin and (C) the photopolymerization initiator are not used together, there are no problems with dispersibility (over time) or stability over time in the external appearance of the composition, but the main composition and curing agent composition of Comparative Example 3 Since none of the compositions contained the essential component (E) silica, crawling and pinholes occurred during formation of dry films obtained from mixtures thereof. For this reason, since it is clear that Comparative Example 3 is inferior in electrical characteristic evaluation, the same evaluation was not performed.

As described above, the main composition and the curing agent composition of Comparative Examples 1 and 2 had a problem with the combination of the components, respectively, with the passage of time, poor appearance and coarse particles were generated, and the photocurable thermosetting properties of each comparative example were mixtures thereof. It can be seen that the evaluation of crawling and the like at the time of formation of a dry film obtained from the resin composition and the electrical properties are clearly inferior compared to those of Examples.

Claims (8)

(A) an epoxy resin, (B) a carboxyl group-containing resin, (C) a photopolymerization initiator, (D) a photosensitive monomer, (E) silica, (F) a photocurable thermosetting resin composition containing barium sulfate and an organic solvent,
In order to obtain the photocurable thermosetting resin composition, it is composed of at least a two-component resin composition,
The (B) carboxyl group-containing resin, the (D) photosensitive monomer, and the (E) silica are contained in a resin composition different from the (A) epoxy resin, the (F) barium sulfate, and the (C) photopolymerization initiator, ,
The resin composition containing the photopolymerization initiator (C) is characterized in that it contains an organic solvent capable of dissolving the photopolymerization initiator (C).
A photocurable thermosetting resin composition composed of at least a two-component resin composition. The photocurable thermosetting resin according to claim 1, characterized in that the (A) epoxy resin contains three types of a semi-solid or solid epoxy resin, a biphenyl type epoxy resin and a novolac type epoxy resin at room temperature. composition. The method according to claim 1 or 2, wherein the resin composition containing the epoxy resin (A) has a viscosity of 4 dPa·s or less, and the photocurable thermosetting resin composition obtained by mixing the respective resin compositions has a viscosity of 4 dPa·s or less. Characterized in that it has a viscosity of, a photocurable thermosetting resin composition. The resin composition according to any one of claims 1 to 3, wherein the resin composition containing the (A) epoxy resin contains the (C) photopolymerization initiator and the organic solvent, and 1 part by mass of the (C) photopolymerization initiator A photocurable thermosetting resin composition characterized by containing 3 parts by mass or more of the organic solvent with respect to A dry film having a film thickness of 10 μm to 30 μm obtained by applying the photocurable thermosetting resin composition according to any one of claims 1 to 4 to a carrier film and drying it. A cured product obtained by curing the photocurable thermosetting resin composition according to any one of claims 1 to 4. A cured product characterized in that it is obtained by curing the resin layer of the dry film according to claim 5. An electronic component characterized by having the cured product according to claim 6 or 7.