KR20080005871A - Photocurable/thermosetting resin composition, cured product thereof and printed wiring board - Google Patents

Abstract

A photocurable/thermosetting resin composition is provided to be superior in soldering heat resistance, adhesion, an electric insulating property, and HAST resistance, to ensure low cure shrinkage, and to produce a substrate without bending even when an extremely thin core material is used. A photocurable/thermosetting resin composition includes any one selected from (A-1) a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride(d) with a reaction product of an epoxy compound(a), a compound(b), and an unsaturated group-containing monocarboxylic acid(c), (A-2) a carboxyl group-containing photosensitive resin obtained by reacting a phenolic hydroxy group-containing compound(e) with alkyleneoxide(f) or a cyclo carbonate compound(g), and reacting the reaction product with an unsaturated group-containing monocarboxylic acid(c) and a polybasic acid anhydride(d), and (A-3) a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride(d) with a reaction product of a linear polyfunctional epoxy compound(h) and an unsaturated group-containing monocarboxylic acid(c), (B) a carboxy group-containing urethane(meth)acrylate compound, (C) a photopolymerization initiator, (D) a thermosetting component, and (E) a diluent.

Description

Photocurable thermosetting resin composition, its hardened | cured material, and printed wiring board {PHOTOCURABLE / THERMOSETTING RESIN COMPOSITION, CURED PRODUCT THEREOF AND PRINTED WIRING BOARD}

[Patent Document 1] Japanese Unexamined Patent Publication No. 2002-229201 (Patent Claims)

[Patent Document 2] Japanese Unexamined Patent Publication No. 2003-192760 (claims)

[Patent Document 3] Japanese Unexamined Patent Application Publication No. 2001-278947 (Patent Claims)

TECHNICAL FIELD The present invention relates to a photocurable and thermosetting resin composition, a cured product thereof, and a printed wiring board useful for the production of semiconductor package substrates used in small, lightweight electronic devices.

Recently, electronic devices tend to be compact, light weight, high performance, and multifunctional, as represented by mobile phones. In response, semiconductor integrated circuits (hereinafter, referred to as ICs) used in these electronic devices are also highly integrated, miniaturized, Thinning is required. In response to these demands, a package containing a semiconductor IC is also coated with a solder resist instead of an IC package called QFP (quad flat pack package), SOP (small outline package), etc. using a lead frame and a sealing resin. An IC package called BGA (ball grid array) or CSP (chip scale package) using an insulating substrate and a sealing resin has emerged. In such a package, a ball-shaped solder is arranged on one side of an insulated printed substrate coated with a solder resist, the IC chip is fused on the other side, and a terminal or a circuit on the printed substrate is formed by wire bonding or bumping. Was electrically connected, and the IC chip was sealed by resin.

As described above, the IC package having such a structure requires miniaturization and thinning, and as a result, the core material forming the printed board on which the IC chip is mounted is also required to be thinned. For example, in a package called UT-CSP, that is, an ultra thin chip scale package, a glass epoxy substrate having a thickness of 30 to 60 µm is used as the core material. As the manufacturing process of such an IC package, a part except these solder balls and wiring patterns on both surfaces of the core material constituting the substrate, that is, the surface on which the solder balls are fixed, and the other surface on which the wiring for connection to the input / output terminals of the IC chip is formed. The resist ink is applied so as to cover the film and then cured to form an insulating protective film. However, as described above, when the substrate is very thin, the shrinkage or undulation of the substrate occurs due to the curing shrinkage during firing of the resist coated on the surface of the core material, which causes problems in chip mounting. In addition, the manufacturing process of IC package also includes the process of exposing a printed board to high temperature, for example, 170-270 degreeC, such as a mold process or a solder adhesion process. For this reason, the resist material requires high reliability such as electrical properties and HAST characteristics (Highly Accelerated Temperature and Humidity Stress Test) together with high heat resistance such as solder heat resistance.

In addition, as the core material becomes thinner, bending due to curing shrinkage of the resist has been a problem. In the case of using such a core material, a roll-to-roll method was used, and a dry film type solder resist was required in view of workability, reliability, film thickness precision, and smoothness. Moreover, such a dry film type soldering resist was supplied in the form of a sheet or a roll, and it was necessary to contain the resin component excellent in flexibility and film forming property in the resin composition in the characteristic in the form.

Conventionally, in order to prevent the bending and undulation of a printed board, it was known to use the photosensitive resin composition containing the urethane (meth) acrylate compound excellent in flexibility as a soldering resist ink with low hardening shrinkage at the time of sintering (patent document) 1). However, although the soldering resist using this photosensitive resin can prevent the bending and undulation of a printed board, it cannot bear the high temperature heat processing in the manufacturing process of an IC package mentioned above, and the necessary electrical property is not acquired. There was this.

Moreover, the compound which has a polymerizable unsaturated group, a carboxyl group, and 1 or more hydroxyl groups in 1 molecule conventionally in the terminal isocyanate compound of the reaction product of the compound, the diol compound, and the polyisocyanate compound which has at least 1 carboxyl group and 2 hydroxyl groups in 1 molecule. The soldering resist containing the photosensitive resin obtained by making it react is proposed (refer patent document 2). However, such a photosensitive resin also had a problem that the heat resistance required for the high temperature heat treatment as described above was insufficient.

On the other hand, the photosensitive resin composition for soldering resists excellent in heat resistance, adhesiveness, and electrical insulation was also known conventionally (refer patent document 3). This resin was excellent in heat resistance, adhesiveness, and electrical insulation, and was useful for a conventional package substrate using a core material with a certain thickness, but satisfies the requirement of preventing warpage and undulation for a very thin core material as described above. It was difficult to make.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and its object is to provide excellent solder heat resistance, adhesion, electrical insulation, and HAST resistance required for solder resists, especially for semiconductor package substrates, while also having low curing shrinkage and extremes. It is providing the photocurable thermosetting resin composition, its hardened | cured material, and printed wiring board which can provide the board | substrate which does not bend also about a thin core material.

In order to achieve the above object, as a basic aspect of the present invention,

(A-1) Epoxy compound (a) which has two or more epoxy groups in 1 molecule, Compound (b) which has one reactor which reacts with one or more alcoholic hydroxyl groups and epoxy groups other than this alcoholic hydroxyl group in 1 molecule, Carboxyl group-containing photosensitive resin obtained by making polybasic acid anhydride (d) react with reaction product with unsaturated group containing monocarboxylic acid (c),

(A-2) A reaction product obtained by reacting a compound (e) having two or more phenolic hydroxyl groups in one molecule with an alkylene oxide (f) or a cyclocarbonate compound (g) and an unsaturated group-containing monocarboxylic acid carboxyl group-containing photosensitive resin obtained by making polybasic acid anhydride (d) react with reaction product with (c), and

(A-3) Linear polyfunctional epoxy compound (h) obtained by alternating polymerization of a bifunctional epoxy compound and a compound having two reactors capable of reacting with an epoxy group, and reacting epihalohydrin with the resulting hydroxyl group Carboxyl group-containing photosensitive resin obtained by making polybasic acid anhydride (d) react with reaction product with unsaturated group containing monocarboxylic acid (c).

 Any one or two or more of

(B) carboxyl group-containing urethane (meth) acrylate compound,

(C) photoinitiator,

(D) a thermosetting component having two or more cyclic ether groups and / or cyclic thioether groups in one molecule, and

(E) thinner

It provides a photocurable, thermosetting resin composition characterized in that it contains.

In addition, the composition

(F) curing catalyst

It provides a photocurable, thermosetting resin composition characterized in that it contains.

As another aspect, after diluting the said photocurable thermosetting resin composition with the organic solvent (E-1) on a carrier film, it apply | coats on a carrier film, is obtained by volatilizing and drying an organic solvent (E-1). Dry film is provided.

Furthermore, the soldering resist film as a permanent protective film was formed on the hardened | cured material and the circuit board which has a patterned conductor layer obtained by hardening the said photocurable thermosetting resin composition by active energy ray irradiation and / or heating. The printed wiring board WHEREIN: The said soldering resist film contains the cured coating film of the said photocurable thermosetting resin composition, The printed wiring board is provided.

Best Mode for Carrying Out the Invention

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject,

(A-1) Epoxy compound (a) which has two or more epoxy groups in 1 molecule, Compound (b) which has one reactor which reacts with one or more alcoholic hydroxyl groups and epoxy groups other than this alcoholic hydroxyl group in 1 molecule, Carboxyl group-containing photosensitive resin obtained by making polybasic acid anhydride (d) react with reaction product with unsaturated group containing monocarboxylic acid (c),

(A-2) A reaction product obtained by reacting a compound (e) having two or more phenolic hydroxyl groups in one molecule with an alkylene oxide (f) or a cyclocarbonate compound (g) and an unsaturated group-containing monocarboxylic acid carboxyl group-containing photosensitive resin obtained by making polybasic acid anhydride (d) react with the reaction product with (c), and

(A-3) Linear polyfunctional epoxy compound (h) obtained by alternating polymerization of a bifunctional epoxy compound and a compound having two reactors capable of reacting with an epoxy group, and reacting epihalohydrin with the resulting hydroxyl group Carboxyl group-containing photosensitive resin obtained by making polybasic acid anhydride (d) react with reaction product with unsaturated group containing monocarboxylic acid (c).

 Any one or two or more of

(B) carboxyl group-containing urethane (meth) acrylate compound,

(C) photoinitiator,

(D) a thermosetting component having two or more cyclic ether groups and / or cyclic thioether groups in one molecule, and

(E) thinner

It has been found that the photocurable and thermosetting resin composition containing a resin can provide a substrate excellent in solder heat resistance, adhesion, electrical insulation, and HAST resistance, and having low curing shrinkage and no warpage. The invention has been completed.

That is, a carboxyl group-containing photosensitive resin (any one or two or more of A-1, A-2, and A-3) having excellent solder heat resistance, adhesion, electrical insulation, and HAST resistance, and a hardening shrinkage and a warp-free substrate By using together the said carboxyl group-containing urethane (meth) acrylate compound (B) which can provide, it was discovered that the objective of this invention can be achieved, without reducing mutual characteristic.

In order to achieve the said objective, the compounding ratio of the said carboxyl group-containing photosensitive resin (A-1, A-2, A-3 or more types) and the said carboxyl group-containing urethane (meth) acrylate compound (B) It is preferable to mix | blend silver in the ratio of 85: 15-15: 85.

In the case of focusing on solder heat resistance, adhesion, electrical insulation and HAST resistance, the ratio of the carboxyl group-containing photosensitive resin (any one or two or more of A-1, A-2 and A-3) is high within the above range. In the case where the cure shrinkage is small and the bending-free characteristic is emphasized, the ratio of the carboxyl group-containing urethane (meth) acrylate compound (B) can be increased within the above range.

When the ratio of the carboxyl group-containing photosensitive resin (any one or two or more of A-1, A-2, and A-3) is higher than 85 mass%, the warpage becomes worse. On the contrary, if the ratio is lower than 15 mass%, heat resistance is poor. It is not desirable because it falls out.

In addition, in this specification, a carboxyl group-containing urethane (meth) acrylate compound is a term used as a general term for a carboxyl group-containing urethane acrylate compound, a carboxyl group-containing urethane methacrylate compound, and mixtures thereof, and the same is true for other similar expressions.

Hereinafter, the structural component of the photocurable thermosetting resin composition of this invention is demonstrated in detail. First, the carboxyl group-containing photosensitive resin (A-1), (A-2), and (A-3) of this invention are demonstrated.

The carboxyl group-containing photosensitive resin (A-1) includes an epoxy compound (a) having two or more epoxy groups in one molecule (hereinafter may be referred to as a polyfunctional epoxy resin), one or more alcoholic hydroxyl groups and an alcoholic property in one molecule. It is a carboxyl group-containing photosensitive resin obtained by making a polybasic acid anhydride (d) react with the reaction product of the compound (b) which has one reactor which reacts with epoxy groups other than a hydroxyl group, and an unsaturated group containing monocarboxylic acid (c).

This carboxyl group-containing photosensitive resin (A-1) has a photosensitive density compared with resin which made polybasic acid anhydride (d) react after making only polyunsaturated group-containing monocarboxylic acid (c) react with polyfunctional epoxy resin (a). It is low and there exists a characteristic that there is little distortion of hardened | cured material.

Furthermore, the compound (b) and the unsaturated group containing monocarboxylic acid (c) which have one reactor which react with one or more hydroxyl groups and epoxy groups other than this hydroxyl group are reacted with a polyfunctional epoxy compound (a). By introducing a photosensitive unsaturated group and a primary hydroxyl group into the epoxy resin skeleton, a polybasic acid anhydride is then added to the primary hydroxyl group which is difficult to separate the acid anhydride, thereby obtaining a resin having excellent HAST resistance and the like.

Next, the carboxyl group-containing photosensitive resin (A-2) is a reaction obtained by reacting a compound (e) having two or more phenolic hydroxyl groups with an alkylene oxide (f) or a cyclocarbonate compound (g) in one molecule. It is a carboxyl group-containing photosensitive resin obtained by making a polybasic acid anhydride (d) react with the product and reaction product of an unsaturated group containing monocarboxylic acid (c).

This carboxyl group-containing photosensitive resin (A-2) has a main chain by addition reaction of the compound (e) which has two or more phenolic hydroxyl groups in 1 molecule, and an alkylene oxide (f) or a cyclocarbonate compound (g). Resin which has a phenolic hydroxyl group in the position away from this is obtained, and after giving photosensitive by esterification of a part of this phenolic hydroxyl group and an unsaturated group containing monocarboxylic acid (c), some or all of the remaining phenolic hydroxyl groups are given. It is a resin to which polybasic acid anhydride (d) is added to, and since it has a photosensitive unsaturated group in the position away from the main chain, it is excellent in light reactivity, and since there is a free carboxyl group in the position away from the main chain, there is little cleavage after crosslinking, It is possible to provide a cured product having excellent properties and HAST resistance.

In addition, the carboxyl group-containing photosensitive resin (A-3) is a linear product obtained by alternately polymerizing a compound having two reactors capable of reacting with a bifunctional epoxy compound and an epoxy group, and reacting epihalohydrin with the resulting hydroxyl group. It is a linear carboxyl group-containing photosensitive resin obtained by making polybasic acid anhydride (d) react with the reaction product of a polyfunctional epoxy compound (h) and an unsaturated group containing monocarboxylic acid (c).

Since this carboxyl group-containing photosensitive resin (A-3) is based on a linear polyfunctional epoxy compound, it is rich in flexibility and is a bifunctional aromatic epoxy compound, a bifunctional phenolic compound, and / or an aromatic dicarboxyl as a preferred raw material. By using an acid, hardened | cured material which is excellent in water resistance and excellent in an electrical property and HAST tolerance can be provided.

As an epoxy compound (a) which has two or more epoxy groups in 1 molecule used for the synthesis | combination of the said carboxyl group-containing photosensitive resin (A-1), a well-known conventional polyfunctional epoxy compound, for example, bisphenol-A epoxy resin, bisphenol F Type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, bixylenol type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy The resin, the novolak-type epoxy resin of bisphenol A, the copolymer resin of glycidyl (meth) acrylate, etc. are mentioned. Among these, it is preferable to use a phenol novolak-type epoxy resin or a cresol novolak-type epoxy resin, especially the cresol novolak-type epoxy resin with a softening point of 50 degreeC or more from the heat resistance and the photosensitivity of obtained resin.

Moreover, as a compound (b) which has one or more hydroxyl groups and one reactor which reacts with an epoxy group other than this hydroxyl group in 1 molecule used for the synthesis | combination of the said carboxyl group-containing photosensitive resin (A-1), for example, glycolic acid Hydroxy-containing monocarboxylic acids such as dimethylol acetic acid, dimethylol propionic acid, dimethylol butanoic acid, dimethylol valeric acid and dimethylol caproic acid; Dialkanolamines such as diethanolamine and diisopropanolamine; Hydroxymethyl-di-t-butylphenol, p-hydroxyphenethyl alcohol, p-hydroxyphenyl-3-propanol, p-hydroxyphenyl-4-butanol, hydroxyethylcresol, 2,6-dimethyl- 4-hydroxymethylphenol, 2,4-dihydroxymethyl-2-cyclohexylphenol, trimethylolphenol, 3,5-dimethyl-2,4,6-trihydroxymethylphenol, bis (hydroxymethyl) Bis (hydroxyalkyl) phenols, such as a phenol and bis (hydroxymethyl) cresol, are mentioned. Particularly preferred are dimethylolpropionic acid, dimethylolbutanoic acid and p-hydroxyphenethyl alcohol.

Since such a compound has a primary hydroxyl group, compared with the secondary hydroxyl group obtained by reaction of an epoxy group and an unsaturated group containing monocarboxylic acid, the polybasic acid anhydride (d) added after this becomes difficult to separate even under high temperature, high humidity.

Examples of the unsaturated group-containing monocarboxylic acid (c) used in the synthesis of the carboxyl group-containing photosensitive resin (A-1), (A-2) and (A-3) include acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. , Cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic acid, or 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl The compound etc. which added dibasic acid anhydride to the hydroxyl-containing (meth) acrylate compounds, such as (meth) acrylate, a trimethylolpropane di (meth) acrylate, and a pentaerythritol tri (meth) acrylate, are mentioned. have. Among these, acrylic acid or methacrylic acid is preferable in view of reactivity. These unsaturated group containing monocarboxylic acids can also be used individually or in combination of 2 or more types.

Examples of the polybasic acid anhydride (d) used in the synthesis of the carboxyl group-containing photosensitive resins (A-1), (A-2) and (A-3) include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and hexahydro. Phthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, nadic anhydride, octenyl anhydrous succinic acid, pentadodecenyl anhydrous succinic acid, 3,6-endomethylene tetrahydrophthalic anhydride, methyl endomethylene tetra Anhydrides of dibasic or tribasic acids such as hydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, or biphenyltetracarboxylic dianhydride, diphenylethertetracarboxylic dianhydride, butanetetracarboxylic acid Aliphatic or aromatic tetrabasic dianhydrides such as dianhydrides, cyclopentanetetracarboxylic dianhydrides, pyromellitic anhydrides, and benzophenonetetracarboxylic dianhydrides; A can be mentioned, it can be used alone or in combination of two or more of them. Of these, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and succinic anhydride are preferred in view of developability and coating film properties of the cured product.

The addition amount of these polybasic acid anhydrides (d) is the range whose acid value of the carboxyl group-containing photosensitive resin (A-1, A-2, A-3) used by this invention becomes 30-100 mgKOH / g, More preferably, It is the range used as 40-80 mgKOH / g. When polybasic acid anhydride (d) is added so that acid value may become less than the said range, since developability by a diluted alkali aqueous solution falls or heat resistance falls, it is unpreferable. On the other hand, when polybasic acid anhydride (d) is added so that it may become higher than the said range, since developability falls, electrical insulation, electroless plating tolerance, etc. fall, it is unpreferable.

Next, as a compound (e) which has two or more phenolic hydroxyl groups in 1 molecule used for the synthesis | combination of the said carboxyl group-containing photosensitive resin (A-2), catechol, resorcinol, hydroquinone, dihydroxytoluene, naphthalene Diol, t-butylcatechol, t-butylhydroquinone, pyrogallol, phloroglucinol, bisphenol A, bisphenol F, bisphenol S, biphenol, bixylenol, novolac phenol resin, novolac alkylphenol resin, Novolak resin of bisphenol A, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, polyvinyl phenol, condensate of phenols with aromatic aldehyde having phenolic hydroxyl group, 1-naphthol Or a condensate of 2-naphthol and aromatic aldehydes, but is not limited thereto. These phenolic hydroxyl group containing compounds can be used individually or in mixture of 2 or more types.

Examples of the alkylene oxide (f) used in the synthesis of the carboxyl group-containing photosensitive resin (A-2) include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran and the like.

In addition, as a cyclocarbonate compound (g), a well-known conventional carbonate compound can be used, For example, ethylene carbonate, a propylene carbonate, butylene carbonate, 2, 3- carbonate Propyl methacrylate etc. are mentioned, Preferably, 5-membered ring ethylene carbonate and propylene carbonate are preferable at the point of reactivity and a supply system.

These alkylene oxides (f) or cyclocarbonate compounds (g) can be used individually or in mixture of 2 or more types.

The alkylene oxide (f) or the cyclocarbonate compound (g) can be modified to a resin having an alcoholic hydroxyl group from the phenolic hydroxyl group by addition reaction using a basic catalyst to the phenolic hydroxyl group of the phenolic hydroxyl group-containing compound. . As addition amount at this time, it is the range of 0.3-10 mol per equivalent of phenolic hydroxyl group, Preferably it is the range of 0.8-5 mol, More preferably, it is the range of 1.0-3 mol.

When the addition amount is less than the above range, the reaction with the unsaturated group-containing monocarboxylic acid (c) or polybasic anhydride (d) is less likely to occur, which is not preferable because the solubility in photosensitive and dilute aqueous alkali solution is lowered. On the other hand, when addition amount exceeds the said range, since water resistance falls by the ether bond produced | generated and electrical insulation, HAST tolerance, etc. fall, it is unpreferable.

As a basic catalyst used for the said reaction, alkali metal compounds, such as potassium carbonate, sodium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, tertiary amines, such as triethylamine, and 2-ethyl-4-methylimidazole Imidazole compounds such as these, phosphorus compounds such as triphenylphosphine, tetramethylammonium chloride, tetrabutylammonium bromide, trimethylbenzyl ammonium halide, tetramethylammonium benzoate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, Quaternary basic salt compounds such as tetramethylphosphonium hydroxide, naphthenic acid, lauric acid, stearic acid, metal salts of organic acids such as lithium, chromium, zirconium, potassium and sodium of oleic acid and octoenoic acid are preferably used. do. These catalysts can be used individually or in mixture of 2 or more types.

It is preferable to perform the said reaction at normal temperature-250 degreeC using such a basic catalyst. As the reaction solvent, benzene, toluene, xylene, tetramethylbenzene, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, octane, methyl isobutyl ketone, diisopropyl ether and the like are preferably used. These organic solvents can be used individually or in mixture of 2 or more types.

As a bifunctional epoxy compound used for the synthesis | combination of the said carboxyl group-containing photosensitive resin (A-3), 1, 6- hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, a biphenol type diglycidyl ether And bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthalene-type diglycidyl ether, but a biphenol having an aromatic ring represented by the following general formulas (1) to (4): One monomer in alternating copolymers with one or more difunctional aromatic alcohols such as diglycidyl ether, bixylenol diglycidyl ether, bisphenol diglycidyl ether, and naphthalene diglycidyl ether By setting it as a component, the epoxy compound excellent in the intensity | strength, heat resistance, electrical insulation, etc. of hardened | cured material is obtained.

As such non-phenolic, bixylenol-type, bisphenol-type or naphthalene-type diglycidyl ethers, for example, from the reaction of a biphenol compound, bixylenol compound, bisphenol compound or dihydroxynaphthalene with epichlorohydrin What is produced can be used. Moreover, a commercial epoxy compound can also be used, For example, As a biphenol type diglycidyl ether, As a bixylenol type diglycidyl ether, such as Yuka-Shell Epoxy Co., Ltd. brand name "Epicoat YL-6056", As bisphenol-type diglycidyl ether, such as the brand name "Epicoat YX-4000" of Yuka Shell Epoxy Co., Ltd. product name "Araldite # 260" of Asahi Shiva Co., Ltd., "Araldite # 6071", etc. Bisphenol F type epoxy compounds, such as the bisphenol A type epoxy compound or the brand name "Epiclon 830S" of the Dainippon ink Kagaku Kogyo Co., Ltd. or brand name "Epiclon EXA1514 of the Dainippon Ink Chemical Co., Ltd." As bisphenol S-type epoxy compounds and naphthalene type diglycidyl ether, etc., the brand name "Epiclon HP-4032 (D)" of Dainippon Ink & Chemicals Co., Ltd. product, etc. are mentioned, These are independentlyIt may be used in combination of two or more. Biphenol type diglycidyl ether, bixenol type diglycidyl ether, bisphenol type diglycidyl ether, naphthalene type diglycidyl ether, etc. which have an aromatic ring are preferable. These bifunctional epoxy compounds can be used individually or in mixture of 2 or more types.

As a compound which has two reactors which can react with the epoxy group used for the synthesis | combination of the said carboxyl group-containing photosensitive resin (A-3), a difunctional phenol compound, dicarboxylic acid, the amine compound which has two active hydrogens, and dithiol Although a compound etc. are mentioned, A bifunctional phenolic compound and dicarboxylic acid are preferable because of resin stability and the ease of reaction.

As a bifunctional phenolic compound, the structure has the characteristics, and in order to improve heat resistance, what has an aromatic ring and has a symmetrical structure or a rigid structure can be used. As such a compound, it is 1, 4- dihydroxy naphthalene, 1, 5- dihydroxy naphthalene, 1, 6- dihydroxy naphthalene, 2, 6- dihydroxy naphthalene, 2, 7- dihydroxy, for example. Dihydroxynaphthalene derivatives such as naphthalene and 2,8-dihydroxynaphthalene, biphenol derivatives such as bixylenol, biphenol, bisphenol derivatives such as bisphenol A, bisphenol F, bisphenol S, alkyl-substituted bisphenol, hydroquinone and methyl Hydroquinone derivatives, such as hydroquinone and a trimethyl hydroquinone, etc. are mentioned, These can be used individually or in combination of 2 or more types.

As dicarboxylic acid, succinic acid, fumaric acid, phthalic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and pyromellitic dianhydride and Tetrabasic dianhydrides, such as benzophenone tetracarboxylic dianhydride, and half ester, such as 2-hydroxymethyl (meth) acrylate, etc. are mentioned.

As a catalyst used for reaction of a bifunctional epoxy compound and a bifunctional phenolic compound or dicarboxylic acid, phosphine, an alkali metal compound, and amine which a glycidyl group and a phenolic hydroxyl group or a carboxyl group react quantitatively individually or use together It is preferable to use. A catalyst other than this is not preferable because it reacts with an alcoholic hydroxyl group produced by the reaction of glycidyl group and phenolic hydroxyl group and gelates.

Examples of the phosphines include trialkyl or triaryl phosphines such as tributyl phosphine and triphenyl phosphine, salts of these and oxides, and the like. Examples of the alkali metal compound include hydroxides, halides, alcoholates, and amides of alkali metals such as sodium, lithium, and potassium, and these may be used alone or in combination of two or more thereof.

Examples of the amines include aliphatic or aromatic primary, secondary, tertiary and quaternary amines, and these may be used alone or in combination of two or more thereof. Specific examples of the amines include triethanolamine, N, N-dimethylpiperazine, triethylamine, tri-n-propylamine, hexamethylenetetramine, pyridine, tetramethylammonium bromide and the like.

These catalysts are preferably used in the range of 0.001 to 1 parts by mass, preferably 0.01 to 1 parts by mass with respect to 100 parts by mass of the bifunctional epoxy compound and the bifunctional phenol compound or dicarboxylic acid. This reason is not preferable because when the amount of the catalyst used is less than 0.001 part by mass, the reaction takes time and is not economical.

The bifunctional aromatic epoxy resin compound and the difunctional phenolic compound or dicarboxylic acid are preferably reacted in an inert gas stream or in the air at a temperature in the range of 130 ° C to 180 ° C.

The linear polyfunctional epoxy compound (h) is a known solvent such as aprotic polar solvents such as dimethyl sulfoxide, N, N-dimethylformamide and N, N-dimethylacetamide, and aromatic hydrocarbons such as toluene and xylene. In the presence of an alkali metal hydroxide, it can manufacture by making it react with an alcoholic hydroxyl group and epihalohydrin in the reaction product with the bifunctional epoxy compound mentioned above, a bifunctional phenolic compound, or dicarboxylic acid.

As said epihalohydrin, for example, epichlorohydrin, epibromohydrin, epiiodohydrin, (beta) -methyl epichlorohydrin, (beta) -methyl epibromohydrin, (beta) -methyl epiiodohihi Used are used.

In the linear polyfunctional epoxy compound (h), the amount of epihalohydrin used is relative to 1 equivalent of the alcoholic hydroxyl group in the reaction product of the bifunctional epoxy compound described above and the difunctional phenol compound or dicarboxylic acid. About 0.1 times or more can be used. However, use of the amount exceeding 15 times equivalent with respect to 1 equivalent of hydroxyl groups is bad in volume efficiency worsening.

Moreover, as alkali metal hydroxide, caustic soda, caustic kali, lithium hydroxide, calcium hydroxide, etc. can be used, Especially caustic soda is preferable. It is preferable that the usage-amount of this alkali metal hydroxide is 0.5 to 2 times equivalent with respect to 1 equivalent of the alcoholic hydroxyl group to epoxidize in the reaction product of the said bifunctional aromatic epoxy compound and the said bifunctional aromatic alcohol.

It is preferable that the reaction temperature of an alcoholic hydroxyl group and epihalohydrin in the reaction product of a bifunctional aromatic epoxy compound, a bifunctional phenolic compound, or dicarboxylic acid is 20-100 degreeC. The reason is that if the reaction temperature is less than 20 ° C, the reaction is delayed and a long time reaction is required. On the other hand, if the reaction temperature exceeds 100 ° C, many side reactions occur, which is not preferable.

The reaction between the alcoholic hydroxyl group and the epihalohydrin in the reaction product of the difunctional aromatic epoxy compound with the difunctional phenol compound or dicarboxylic acid is dimethyl sulfoxide or quaternary ammonium salt or 1,3- It can also be performed by adjusting the quantity of the said alkali metal hydroxide in the coexistence of dimethyl-2-imidozoline and an alkali metal hydroxide. In that case, you may use together alcohols, such as methanol and ethanol, aromatic hydrocarbons, such as toluene and xylene, ketones, such as methyl isobutyl ketone and methyl ethyl ketone, and cyclic ether compounds, such as tetrahydrofuran, as a solvent.

Examples of quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, trimethylammonium chloride, and the like, and the amount of the quaternary ammonium salts thereof is based on 1 equivalent of the hydroxyl group to be epoxidized of the epoxy resin used as a raw material. 0.3-50 g is preferable. When it is less than 0.3 g with respect to 1 equivalent of hydroxyl group to epoxidize, since the reaction of the alcoholic hydroxyl group and epihalohydrin of the epoxy resin used as a raw material is delayed, long time reaction is needed, and it is not preferable. On the other hand, when it exceeds 50 g with respect to 1 equivalent of hydroxyl group to epoxidize, it is unpreferable since the cost is high and there is little increase in hardening.

In the reaction of the linear polyfunctional epoxy compound (h) with an unsaturated group-containing monocarboxylic acid (c) to obtain a compound with an unsaturated epoxy acrylate, to the linear polyfunctional epoxy compound (h), the compound Unsaturated group-containing monocarboxylic acid is mix | blended in the ratio of 0.8-1.3 mol with respect to 1 mol of epoxy groups contained in it, and it heats at 60-150 degreeC, Preferably it is 70-130 degreeC in an inert solvent or a solvent, Preferably Reacts in the presence of air. Hydroquinones, such as methyl hydroquinone and hydroquinone, in order to prevent gelation by superposition | polymerization in reaction; It is preferable to use well-known conventional polymerization inhibitors, such as benzoquinones, such as p-benzoquinone and p-tolquinone. Moreover, in order to shorten reaction time, it is preferable to use an esterification catalyst, As esterification catalyst, For example, tertiary amines, such as N, N- dimethylaniline, pyridine, triethylamine, and its hydrochloride or bromate; Quaternary ammonium salts such as tetramethylammonium chloride and triethylbenzylammonium chloride; Sulfonic acids such as paratoluenesulfonic acid; Sulfonium salts such as dimethyl sulfoxide and methyl sulfoxide; Phosphines such as triphenylphosphine and tri-n-butylphosphine; Known and conventional ones such as metal halides such as lithium chloride, lithium bromide, first tin chloride and zinc chloride can be used. As inert solvent, toluene, xylene, etc. can be used, for example.

The number average molecular weight of the said carboxyl group-containing photosensitive resin (A-3) is 400-10,000, Preferably it is 500-7,000, More preferably, it is 500-3,000. If the number average molecular weight of the active energy ray-curable resin is less than 400, the toughness of the resulting cured product will not be sufficient, while if it exceeds 10,000, the solubility in the solvent will be deteriorated.

Next, the carboxyl group-containing urethane (meth) acrylate compound (B) which is the 2nd characteristic of this invention is a hydroxyl-group containing (meth) acrylate compound (i), dimethylol alkanoic acid (j), and a diisocyanate compound ( a compound obtained by reacting k) and / or a compound obtained by reacting a hydroxyl group-containing (meth) acrylate compound (i), dimethylolalkanoic acid (j), a diisocyanate compound (k) and a polymer polyol (m) And an acid value of 30 to 100 mgKOH / g.

Since the carboxyl group-containing urethane (meth) acrylate compound (B) is basically a carboxyl group-containing photosensitive resin having a linear urethane bond, the carboxyl group-containing urethane (meth) acrylate compound (B) has flexibility and has an effect of reducing warpage due to curing shrinkage.

The hydroxyl group-containing (meth) acrylate compound (i) used for the synthesis of the carboxyl group-containing urethane (meth) acrylate compound (B) is basically a (meth) acrylate compound (i) having one hydroxyl group (i) -1) or (meth) acrylate (i-2) which has two hydroxyl groups.

As a (meth) acrylate compound (i-1) which has one said hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy, for example Butyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and a reaction product of glycidyl (meth) acrylate and (meth) acrylic acid. The (meth) acrylate compound which has one such hydroxyl group functions as a terminator which stops molecular growth in addition to the terminal of the carboxyl group-containing urethane (meth) acrylate compound of this invention.

On the other hand, as (meth) acrylate (i-2) which has two hydroxyl groups, it can be used for the bifunctional epoxy (meth) acrylate compound which added (meth) acrylic acid to the bifunctional epoxy compound, or the bifunctional oxetane compound. The bifunctional oxetane (meth) acrylate compound which added (meth) acrylic acid is mentioned.

Specifically, (meth) acrylates of bifunctional epoxy resins having aromatic rings such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenol type epoxy resins, and bixylenol type epoxy resins desirable. As molecular weight of these bifunctional epoxy (meth) acrylates, it is preferable to fall in the range of 450-2,000 from a viewpoint of a cured coating film characteristic.

The dimethylol alkanoic acid (j) is a compound having two tertiary carboxyl groups and two primary hydroxyl groups, and specific examples thereof include dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolpentanoic acid, and dimethylolhexanoic acid. Among them, dimethylolpropionic acid and dimethylolbutanoic acid are preferred in view of the properties of the cured coating film.

As said diisocyanate compound (k), phenylene diisocyanate, toluylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, trimethylphenylene diisocyanate, diphenylmethane Diisocyanate, dicyclohexyl methane diisocyanate, tetramethyl xylylene diisocyanate, etc. are mentioned. Among these, especially isophorone diisocyanate is preferable because reaction control is easy.

In the synthesis of the carboxyl group-containing urethane (meth) acrylate compound (B) used in the photocurable and thermosetting resin composition of the present invention, a polymer polyol (m) may be further used in order to reduce curing shrinkage.

As said polymer polyol (m), although the diol compound which is hard to be three-dimensionalized fundamentally is preferable, Triol can also be added in order to have a branched structure. Specifically, polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene glycols, etc. are mentioned.

In particular, polycarbonate polyols derived from diols or bisphenols and carbonate esters such as dimethyl carbonate are preferable in view of chemical resistance and the like.

These hydroxyl group-containing (meth) acrylate compounds (i), the dimethylol alkanoic acid (j), the diisocyanate compound (k), or the polymer polyol (m) are further urethaneized by known methods. The carboxyl group-containing urethane (meth) acrylate compound (B) used by this invention can be synthesize | combined.

Specifically, the isocyanate group and hydroxyl group have an equivalent ratio of 0.8 to 1.05, and the acid value of the resulting carboxyl group-containing urethane (meth) acrylate compound (B) is 30 to 100 mgKOH / g and reacted. As reaction conditions, it can synthesize | combine by making it react at normal temperature -150 degreeC, Preferably it is 60-120 degreeC in a solventless or aprotic solvent using the metal catalyst which is hard to three-dimensionalize.

When the acid value of the said carboxyl group-containing urethane (meth) acrylate compound (B) is less than 30 mgKOH / g, since developability by a diluted alkali aqueous solution cannot be obtained, it is not preferable. On the other hand, when the acid value exceeds 100 mgKOH / g, it is not preferable because developing resistance cannot be obtained, or electroless plating resistance and the like are lowered.

(C) photoinitiator is used for the photocurable and thermosetting resin composition of this invention in order to photocure the said carboxyl group-containing photosensitive resin (A) and the said carboxyl group-containing urethane (meth) acrylate compound (B) with good efficiency. do.

As said photoinitiator (C), For example, benzoin and benzoin alkyl ether, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone- Aminoacetophenones such as 1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; Thioxanthones, such as 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, and 2, 4- diisopropyl thioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzyl and benzophenone; Or xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphineoxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine jade Phosphine oxides such as seed, ethyl-2,4,6-trimethylbenzoylphenylphosphinate, (2- (acetyloxyiminomethyl) thioxanthene-9-one), (1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- And oxime esters such as 1- (O-acetyl oxime)).

These known conventional photoinitiators can be used individually or in combination of 2 or more types. Although it is suitable that the compounding ratio of the said photoinitiator (C) is 0.01-30 mass parts with respect to 100 mass parts of total amounts of the said carboxyl group-containing photosensitive resin (A) and the said carboxyl group-containing urethane (meth) acrylate compound (B), In the case of an oxime type photoinitiator, 0.01-20 mass parts, Preferably 0.01-5 mass parts is suitable. When the usage-amount of a photoinitiator is less than the said range, since photocurability worsens and in many cases, a cured coating film characteristic falls, it is unpreferable.

Moreover, the photocurable thermosetting resin composition of this invention can contain a tertiary amine compound and a benzophenone compound as a photoinitiation adjuvant. Examples of such tertiary amines include ethanolamines, 4,4'-dimethylaminobenzophenone (Nissocure MABP manufactured by Nippon Soda Co., Ltd.), ethyl 4-dimethylaminobenzoate (Gayacure EPA manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylamino Ethyl benzoate (Quantacure DMB, manufactured by International Bio-Synthetics Co., Ltd.), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics Co., Ltd.), isoamyl ethyl ester (p-dimethylaminobenzoic acid) Coarse-made Kayacure DMBI), 4-dimethylaminobenzoic acid 2-ethylhexyl (Esolol 507 by Van Dyk), 4,4'- diethylamino benzophenone (EAB by Hodogaya Chemical Co., Ltd.), etc. are mentioned. . These known conventional tertiary amine compounds can be used alone or as a mixture of two or more thereof. Particularly preferred tertiary amine compounds are 4,4'-diethylaminobenzophenone, but are not particularly limited to these, and absorb light in the region having a wavelength of 300 to 420 nm, and exhibit a sensitizing effect by using in combination with a hydrogen emitting photopolymerization initiator. If it exhibits, it is not limited to a photoinitiator and a photoinitiator, It can be used individually or in combination.

In the photocurable and thermosetting resin composition of this invention, in order to improve the heat resistance of hardened | cured material, the said thermosetting component (D) which has 2 or more cyclic ether group and / or cyclic thioether group in 1 molecule (hereinafter, cyclic (thio) ether) May be referred to as a compound).

As the thermosetting component (D) which has two or more cyclic ether groups and / or cyclic thioether group in such 1 molecule, any 1 type of 3, 4 or 5 membered cyclic ether group, or cyclic thioether group in 1 molecule, or A compound having two or more two kinds of groups, for example, a compound having two or more epoxy groups in one molecule, that is, a polyfunctional epoxy compound (D-1), a compound having two or more oxetane groups in one molecule, that is, A functional oxetane compound (D-2) and the compound which has 2 or more thioether group in 1 molecule, ie, episulfide resin, etc. are mentioned.

Examples of the polyfunctional epoxy compound (D-1) include Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, and Dinibon Ink Co., Ltd. Epiclone 840, manufactured by Japan Epoxy Resin Co., Ltd. Epiclone 850, Epiclone 1050, Epiclone 2055, Etoto YD-011, YD-013, YD-127, YD-128 manufactured by Toto Kasei Co., Ltd., DER317, DER331, DER661, manufactured by Dow Chemical Co., Ltd. DER664, Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumiepoxy ESA-011, ESA-014, ELA-115 manufactured by Sumitomo Chemical Co., Ltd. Bisphenol A type epoxy resins such as ELA-128, AER330, AER331, AER661, and AER664 manufactured by Asahi Kasei Kogyo Co., Ltd .; Epicoat YL903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclone 152, Epiclone 165, manufactured by Dainippon Ink & Chemicals Co., Ltd., Efototo YDB-400, YDB-500, manufactured by Toto Kasei Co., Ltd., DER542, manufactured by Dow Chemical Company , Brominated epoxy such as Araldide 8011 manufactured by Shiba Specialty Chemicals, Sumitomo Chemical Co., Ltd., Semiepoxy ESB-400, ESB-700, and Asahi Kasei Kogyo Co., Ltd. Suzy; Epicoat 152, Epicoat 154 manufactured by Japan Epoxy Resin Co., Ltd., DEN431, DEN438 manufactured by Dow Chemical Co., Ltd., Epiclone N-730, Epiclone N-770, Epiclone N- 865, Etoto YDCN-701, YDCN-704 by Toto Kasei Co., Araldide ECN1235 by Ciba Specialty Chemicals, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, Nippon Kayaku Inc. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Kagaku Kogyo Co., Ltd. Sumiepoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo AERECN-235, ECN Novolak-type epoxy resins, such as -299 (all trade names); Epiclone 830, manufactured by Dainippon Ink Industries, Inc., Epicoat 807, manufactured by Japan Epoxy Resin Co., Ltd., Efototo YDF-170, YDF-175, YDF-175, manufactured by Tohto Kasei Co., Ltd., manufactured by Ciba Specialty Chemicals Co., Ltd. Bisphenol F-type epoxy resins, such as Araldide XPY306 (all are brand names); Hydrogenated bisphenol A type epoxy resins such as Efototo ST-2004, ST-2007, ST-3000 (trade name) manufactured by Toto Kasei Co., Ltd .; Epicoat 604 manufactured by Japan Epoxy Resin Co., Ltd., Efototo YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd. Glycidyl amine type epoxy resin of the brand name); Hydantoin type epoxy resins, such as Araldide CY-350 (brand name) by Ciba Specialty Chemicals Co., Ltd .; Alicyclic epoxy resins, such as Celoxide 2021 by Daicel Chemical Industries, Ltd., Araldide CY175 by Ciba Specialty Chemicals, and CY179 (all brand names): YL-933 by Japan Epoxy Resin Co., Ltd., Dow Chemical Co., Ltd. Trihydroxyphenylmethane type epoxy resins such as manufactured TEN, EPPN-501, and EPPN-502 (both trade names); Bixylenol type or biphenol type epoxy resins, such as YL-6056, YX-4000, and YL-6121 (all are brand names) by the Japan epoxy resin company, or mixtures thereof; Bisphenol S type epoxy resins, such as Nippon Kayaku Co., Ltd. EBPS-200, Asahi Denka Kogyo Co., Ltd. EPX-30, and Dai Nippon Ink Chemical Co., Ltd. EXA-1514 (brand name); Bisphenol A novolak-type epoxy resins, such as Epicoat 157S (brand name) by the Japan epoxy resin company; Tetraphenylolethane type epoxy resins, such as Epicoat YL-931 by the Japan epoxy resin company, Araldide 163 by Ciba Specialty Chemicals, Inc. (all are brand names); Heterocyclic epoxy resins such as Araldide PT810 manufactured by Ciba Specialty Chemicals Co., Ltd. and TEPIC manufactured by Nissan Chemical Industries, Ltd. (both trade names); Diglycidyl phthalate resins such as Nippon Yushi Blender DGT; Tetraglycidyl xylenoylethane resins such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .; Naphthalene group-containing epoxy resins such as ESN-190, ESN-360 manufactured by Shin-Nitetsu Chemical Co., Ltd., HP-4032, EXA-4750, and EXA-4700 manufactured by Dainippon Ink & Chemicals Co., Ltd .; Epoxy resin which has dicyclopentadiene frame | skeleton, such as the Dai Nippon Ink Industries Co., Ltd. product HP-7200 and HP-7200H; Glycidyl methacrylate copolymer type epoxy resins such as Nippon Yushi CP-50S and CP-50M; Furthermore, copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (e.g., PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (e.g., YR-102, YR-450, manufactured by Toto Kasei Co., Ltd.), etc. It is not limited to these. These epoxy resins can be used individually or in combination of 2 or more types. Especially among these, a novolak-type epoxy resin, a heterocyclic epoxy resin, a bisphenol-A epoxy resin, or a mixture thereof is preferable.

Examples of the polyfunctional oxetane compound (D-2) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1 , 4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3- Oxetanyl) methylacrylate, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methylmethacrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl methacrylate and oligomers or copolymers thereof, oxetane and novolak resins, poly (p-hydroxystyrene), cardo-type bisphenols, calix arenes and calyx resorcinin And ethers with a resin having a hydroxyl group such as arene or silsesquioxane. In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.

As a compound which has a 2 or more cyclic thioether group in 1 molecule, the bisphenol-A episulfide resin YL7000 by the Japan epoxy resin company, etc. are mentioned, for example. Moreover, the episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can also be used.

The compounding quantity of such a cyclic (thio) ether compound (D) is 0.5-2.0 equivalent with respect to 1 equivalent of the total amount of the carboxyl group of the said carboxyl group-containing photosensitive resin (A) and the said carboxyl group-containing urethane (meth) acrylate compound (B). Is a range of 0.8 to 1.5 equivalents. When the compounding quantity of the said cyclic (thio) ether compound (D) is less than the said range, since a carboxyl group remains and heat resistance, alkali resistance, electrical insulation, etc. fall, it is unpreferable. On the other hand, when the said range is exceeded, since the low molecular weight cyclic (thio) ether compound (D) remains, since the intensity | strength of a coating film, etc. fall, it is unpreferable.

Moreover, the photocurable and thermosetting resin composition of this invention improves photocurability for the synthesis | combination of the said carboxyl group-containing photosensitive resin (A) and the said carboxyl group-containing urethane (meth) acrylate compound (B), or manufacture of a composition. (E) diluent is used to make this work. As the diluent (E), an organic solvent (E-1) can be used as the non-reactive diluent, or a polymerizable monomer (E-2) can be used as the reactive diluent.

Examples of the organic solvent (E-1) include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, 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, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Glycol ethers such as these; Glycol ether acetates such as dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; Esters such as ethyl acetate, butyl acetate and acetate esters of the above glycol ethers: alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These organic solvents (E-1) are used individually or as a mixture of 2 or more types.

Although the compounding quantity of the said organic solvent (E-1) is not specifically limited, Although it can determine in consideration of coating property or the film thickness securing surface of a dry coating film, the said carboxyl group-containing photosensitive resin (A) and the said carboxyl group-containing urethane (meth) acryl 300 mass parts or less are preferable with respect to 100 mass parts of total amounts of a rate compound (B).

Moreover, as said polymerizable monomer (E-2) which is a reactive diluent, Hydroxyalkyl acrylates, such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Mono or diacrylates of glycols such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Polyhydric acrylates such as polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or ethylene oxide adducts or propylene oxide adducts thereof; Acrylates such as phenoxyacrylate, bisphenol A diacrylate and ethylene oxide adducts or propylene oxide adducts of these phenols; Acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; And melamine acrylate, and / or each methacrylate corresponding to the said acrylate etc. are mentioned. Among these, the polyfunctional (meth) acrylate compound which is a compound which has a 2 or more ethylenically unsaturated group in a molecule | numerator is especially preferable because it is excellent in photocurability.

Moreover, pentaerythritol tree to the epoxy acrylate resin which made acrylic acid react with polyfunctional epoxy resins, such as bisphenol A, a bisphenol F-type epoxy resin, a phenol, and a cresol novolak-type epoxy resin, and the hydroxyl group of this epoxy acrylate resin And epoxyurethane acrylate compounds obtained by reacting hydroxyacrylates such as acrylates and half-urethane compounds of diisocyanates such as isophorone diisocyanate. Such epoxy acrylate-based resin can improve the photocurability without deteriorating the touch dryness.

The compounding quantity of the said polymerizable monomer (E-2) is 5-120 mass parts with respect to 100 mass parts of total amounts of the said carboxyl group-containing photosensitive resin (A) and the said carboxyl group-containing urethane (meth) acrylate compound (B), More preferably, Is a ratio of 10 to 70 parts by mass. When the said compounding quantity exceeds 120 mass parts, since electrical insulation etc. fall or a coating film becomes weak, it is unpreferable.

Therefore, as a compounding quantity of all the diluents (E), 300 mass parts of said organic solvents (E-1) with respect to 100 mass parts of total amounts of the said carboxyl group-containing photosensitive resin (A) and the said carboxyl group-containing urethane (meth) acrylate compound (B). It becomes 5-420 mass parts which is a sum total of 5 or 120 mass parts of below and the said polymerizable monomer (E-2).

The photocurable and thermosetting resin composition of this invention is in the carboxyl group of the said carboxyl group-containing photosensitive resin (A-1, A-2, A-3) and the said carboxyl group-containing urethane (meth) acrylate compound (B), and a molecule | numerator In order to accelerate hardening reaction of the said thermosetting component (D) which has two or more cyclic ether group and / or cyclic thioether group, it is preferable to mix | blend a (F) hardening catalyst.

Examples of the curing catalyst (F) include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 4-phenyl. Imidazole derivatives such as midazole, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine Hydrazine compounds such as compounds, adipic acid hydrazide and sebacic acid hydrazide; As commercially available things, such as phosphorus compounds, such as a triphenyl phosphine, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are brand names of an imidazole compound), and San Apro by Shikoku Kasei Kogyo Co., Ltd. U-CAT3503N, U-CAT3502T (all are brand names of the block isocyanate compound of dimethylamine), DBU, DBN, U-CATSA102, and U-CAT5002 (all bicyclic amidine compounds and its salts) etc. are manufactured. It is not specifically limited, It may accelerate | stimulate reaction of the thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group and / or an oxetanyl group, and a carboxyl group, and may be used individually or in mixture of 2 or more types. . In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine and 2-vinyl-2,4-, which also function as an adhesion imparting agent Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-tri S-triazine derivatives, such as azine and isocyanuric acid adduct, can also be used, Preferably, the compound which functions also as these adhesive imparting agents is used together with the above-mentioned thermosetting catalyst.

The compounding quantity of the said curing catalyst (F) is sufficient in a normal quantitative ratio, For example, it is 0.1-20 mass parts with respect to 100 mass parts of total resin compositions, Preferably it is the ratio of 0.5-15.0 mass parts. When the compounding quantity of the said curing catalyst (F) is less than the said range, since hardening time becomes long, workability | operativity falls, oxidation, such as copper foil, becomes unpreferable. On the other hand, when the compounding quantity of the said curing catalyst (F) exceeds the said range, since an electrical property falls or the leaving life after temporary drying becomes short, it is not preferable.

Moreover, an inorganic filler can be further mix | blended with the photocurable thermosetting resin composition of this invention for the purpose of improving the characteristics, such as adhesiveness of hardened | cured material, mechanical strength, a linear expansion coefficient, and the like. For example, known conventional inorganic fillers such as barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide and mica powder can be used. . The compounding ratio is 0-80 mass% of a resin composition.

The photocurable thermosetting resin composition of this invention is known conventional coloring agents, such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black, as needed, Known conventional thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, finely divided silica such as finely divided silica, organic bentonite, montmorillonite, silicone type, fluorine type, polymer type etc. Known conventional additives such as antifoaming agents and / or leveling agents, silane coupling agents such as imidazole series, thiazole series, and triazole series can be further blended.

The photocurable and thermosetting resin composition of this invention is adjusted to the viscosity suitable for an application | coating method with the said diluent (E), for example, and is immersion coating method, flow coating method, roll coating method, bar coating method on the circuit-formed board | substrate. To the entire surface by a method such as a screen printing method or a curtain coating method, and a tack free coating film is formed by volatilizing (drying) the organic solvent contained in the composition at a temperature of 60 to 100 ° C. can do. Thereafter, the photomask having a pattern formed by a contact type (or non-contact method) is selectively exposed by an active energy ray, and the unexposed portion is diluted with a diluted alkali aqueous solution (for example, an aqueous solution of 0.3 to 3% sodium carbonate). It develops and a resist pattern is formed.

As a base material used for the said circuit-formed board | substrate, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven fabric epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine, polyethylene, PPO, cyanate ester, etc. Copper clad laminates, such as copper clad laminates for high frequency circuits, are used, and copper clad laminates of all grades (FR-4, etc.), other polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, and the like can be given.

As aqueous alkali solution, aqueous alkali solution, such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, can be used.

Moreover, as an irradiation light source used for active energy ray irradiation, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. are suitable. In addition, a laser beam etc. can also be used as an active energy ray.

As the developing method, an immersion method, a shower method, a spray method, a brush method, and the like can be used. As the developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia or amines can be used. Can be.

Further, for example, two or more of the carboxyl groups of the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing urethane (meth) acrylate compound (B) by heating at a temperature of 140 to 180 ° C and thermosetting The said thermosetting component (D) which has a cyclic ether group and / or a cyclic thioether group reacts, and can form the cured coating film excellent in various characteristics, such as heat resistance, chemical-resistance, hygroscopicity, adhesiveness, and electrical characteristics.

The case where the photocurable and thermosetting composition of this invention is used as a dry film is shown below.

The photocurable thermosetting dry film has a photocurable thermosetting resin layer obtained by apply | coating and drying a carrier film and the said photocurable thermosetting resin composition to a carrier film or a cover film, and a cover film which can peel on a resin layer. will be.

As a carrier film, polyester films, such as 10-150 micrometers thick PET, a polyimide film, etc. are used.

The photocurable thermosetting resin layer is formed by uniformly applying a photocurable thermosetting composition to a carrier film or cover film with a blade coater, a lip coater, a comma coater, a film coater and the like to a thickness of 10 to 150 µm and drying it.

Although a polyethylene film, a polypropylene film, etc. can be used as a cover film, it is good that adhesive force with a photocurable thermosetting resin layer is smaller than a support film.

The cover film is peeled off, the photocurable thermosetting resin layer and the substrate formed with a circuit are overlapped, and bonded together using a laminating machine or the like to form a photocurable thermosetting resin layer on the circuit formed substrate. The formed photocurable thermosetting resin layer can expose, develop, and heat-cure as mentioned above, and can form a cured coating film. The carrier film can be peeled off at any time before or after exposure.

EXAMPLE

Although an Example and a comparative example are shown to the following and this invention is demonstrated concretely, of course, this invention is not limited to the following Example.

Synthesis Example 1 Synthesis of Carboxyl Group-Containing Photosensitive Resin (A-1) 1

2200 g of cresol novolak-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C, epoxy equivalent 220), 134 g of dimethylolpropionic acid, 648.5 g of acrylic acid, 4.6 g of methyl hydroquinone, 1131 g of carbitol acetate And 484.9 g of solvent naphtha were added, heated to 90 ° C. and stirred to dissolve the reaction mixture. Subsequently, the reaction solution was cooled to 60 ° C, 13.8 g of triphenylphosphine was added thereto, heated to 100 ° C, and reacted for about 32 hours to obtain a reaction product having an acid value of 0.5 mgKOH / g. Subsequently, 364.7 g of tetrahydrophthalic anhydride, 137.5 g of carbitol acetate, and 58.8 g of solvent naphtha were added thereto, and heated to 95 ° C. for about 6 hours to react, followed by cooling to an acid value of 40 mgKOH / g of a nonvolatile content of 65%. Carboxyl group-containing photosensitive resin was obtained. Hereinafter, this reaction solution was called varnish (A-1-1).

Synthesis Example 2 Synthesis of Carboxyl Group-Containing Photosensitive Resin (A-1) 2

2200 g of cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C, epoxy equivalent 220) was placed in a four-necked flask equipped with a stirrer and a cooler, and 2072 g of propylene glycol monomethyl ether acetate After adding and dissolving by heating, 4.6 g of methylhydroquinone and 13.8 g of trimethylphosphine were added. This mixture was heated to 95-105 degreeC, 504 g of acrylic acid and 415 g of p-hydroxy phenethyl alcohol were dripped gradually, and it was made to react for about 16 hours. This reaction was cooled to 80-90 degreeC, 730 g of tetrahydrophthalic anhydride was added to this, and it was made to react for about 8 hours, and it cooled, and obtained the carboxyl group-containing photosensitive resin of 70 mgKOH / g of solids and 65% of non volatile matters. Hereinafter, this reaction solution was called varnish (A-1-2).

Synthesis Example 3: Synthesis of Carboxyl Group-Containing Photosensitive Resin (A-2)

119.4 g of a novolak-type cresol resin (Showa Kohunshi Co., Ltd. make, brand name "Shonol CRG951", OH equivalence: 119.4) in the autoclave provided with the thermometer, the nitrogen introduction apparatus, the alkylene oxide introduction apparatus, and the stirring apparatus. 1.19 g of potassium hydroxide and 119.4 g of toluene were added and nitrogen-substituted in the system, stirring, and heating was heated. Next, 63.8 g of propylene oxide was slowly added dropwise and reacted at 125 to 132 ° C and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the mixture was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide, propylene oxide of a novolak-type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq. The reaction solution was obtained. This was an average of 1.08 mol of alkylene oxide added per 1 equivalent of phenolic hydroxyl group.

293.0 g of the alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were placed in a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was supplied. Blown at a rate of 10 ml / min, and reacted at 110 degreeC for 12 hours, stirring. As for the water produced | generated by reaction, 12.6 g of water flowed out as an azeotropic mixture with toluene. Thereafter, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of an aqueous 15% sodium hydroxide solution, followed by washing with water. Thereafter, toluene was distilled off while replacing toluene with 118.1 g of diethylene glycol monoethyl ether acetate in an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were placed in a reactor equipped with a stirrer, a thermometer, and an air blown tube, and the air was blown at a rate of 10 ml / min, followed by tetra 60.8 g of hydrophthalic anhydride were slowly added and reacted at 95-101 degreeC for 6 hours. The acid value 88 mgKOH / g of solids and the carboxyl group-containing photosensitive resin of 71% of non volatile matter were obtained. Hereinafter, this reaction solution was called varnish (A-2).

Synthesis Example 4: Synthesis of Carboxyl Group-Containing Photosensitive Resin (A-3)

224 parts of 1,5-dihydroxynaphthalene having a hydroxyl equivalent of 80 g / equivalent and bisphenol A in a reaction vessel equipped with a gas introduction tube, a stirring device, a cooling tube, a thermometer, and a dropping funnel for continuous dropping of an aqueous alkali metal hydroxide solution 1075 parts of Epicoat 828 (manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 189 g / equivalent) of an epoxy resin was added thereto, and the mixture was dissolved at 110 ° C under stirring in a nitrogen atmosphere. Thereafter, 0.65 parts of triphenylphosphine was added, the temperature in the reaction vessel was raised to 150 ° C, and reacted for about 90 minutes while maintaining the temperature at 150 ° C to give an epoxy equivalent of 452 g / equivalent epoxy compound (h-0). Got it. Next, the temperature in the flask was cooled to 40 ° C, 1920 parts of epichlorohydrin, 1690 parts of toluene, and 70 parts of tetramethylammonium bromide were added, and the temperature was maintained at 45 ° C under stirring. Thereafter, 364 parts of an aqueous 48% sodium hydroxide solution was added dropwise continuously over 60 minutes, and the mixture was further reacted for 6 hours. After completion of the reaction, most of the excess epichlorohydrin and toluene were recovered by distillation under reduced pressure, and the reaction product containing by-product salt and dimethyl sulfoxide was dissolved in methyl isobutyl ketone and washed with water. After separating an organic solvent layer and an aqueous layer, methyl isobutyl ketone was distilled off under reduced pressure from the organic solvent layer, and the linear polyfunctional epoxy compound (h) of 277 g / equivalent epoxy equivalent was obtained. When the linear polyfunctional epoxy compound (h) obtained was calculated from an epoxy equivalent, about 1.59 of 1.98 alcoholic hydroxyl groups in the epoxy compound (h-0) were epoxidized. Therefore, the epoxidation rate of alcoholic hydroxyl group was about 80%. Next, 277 parts of linear polyfunctional epoxy compounds (h) were put into the flask equipped with a stirring apparatus, a cooling tube, and a thermometer, 290 parts of carbitol acetates were added, it melt | dissolved, and 0.46 parts of methylhydroquinone and 1.38 parts of triphenol phosphines were added. The mixture was heated to 95 to 105 ° C, and 72 parts of acrylic acid was slowly added dropwise and reacted for 16 hours. This reaction product was cooled to 80-90 degreeC, 129 parts of tetrahydrophthalic anhydride were added, and it was made to react for 8 hours. The reaction was traced by the addition rate obtained by performing the acid value of the reaction liquid by potentiometric titration, all oxidation measurement, and made 95% or more of reaction rates into an end point. The carboxyl group-containing photosensitive resin obtained in this way was 62% of solid content, and acid value 100 mgKOH / g. Hereinafter, this reaction solution was called varnish (A-3).

Synthesis Example 5 Synthesis of Urethane (meth) acrylate Compound Having a Carboxyl Group

In a 5 L separable flask equipped with a thermometer, a stirrer and a reflux condenser, 1,245 g of polycaprolactone diol (PLACCEL208, manufactured by Daicel Chemical Industries, Ltd., molecular weight 830) as a polymer polyol, and dimethylolpropionic acid 201 as a dihydroxyl compound having a carboxyl group. g, 777 g of isophorone diisocyanate as polyisocyanate and 119 g of 2-hydroxyethyl acrylate as (meth) acrylate having a hydroxyl group, and also p-methoxyphenol and di-t-butyl-hydroxytoluene 0.5 g each was added. The mixture was heated to 60 ° C. while stirring to stop, and 0.8 g of dibutyltin dilaurate was added. When the temperature in the reaction vessel starts to decrease, heating is continued again and stirring is continued at 80 ° C. The infrared absorption spectrum confirms that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group is lost, and the reaction is terminated. An acrylate compound was obtained. It adjusted to non volatile matter = 50 mass% using PMA. The urethane (meth) acrylate compound which has the acid value of 47 mgKOH / g of solids and the carboxyl group of 50% of non volatile matters was obtained. Hereinafter, this reaction solution was called varnish B.

Synthesis Example 6 Synthesis of General Purpose Carboxyl Group-Containing Photosensitive Resin Different from the Present Invention

330 g of cresol novolac type epoxy resin (Epiclon N-695, manufactured by Dainippon Ink & Chemical Co., Ltd., epoxy equivalent 220) is placed in a flask equipped with a gas introduction tube, a stirring device, a cooling tube, and a thermometer, and 340 g of PMA. It was added to dissolve by heating, 0.46 g of hydroquinone and 1.38 g of triphenylphosphine were added. This mixture was heated to 95-105 degreeC, 108 g of acrylic acid was dripped gradually, and it was made to react for 16 hours. This reaction product was cooled to 80-90 degreeC, 68 g of tetrahydrophthalic anhydrides were added, and it reacted for 8 hours, and cooled. The acid value of 50 mgKOH / g of a solid and the carboxyl group-containing photosensitive resin of 60% of non volatile matters were obtained. Hereinafter, this reaction solution was called varnish R.

Examples 1-12 and Comparative Examples 1-10

It shows in Tables 1-3 using varnishes (A-1-1), (A-1-2), (A-2), (A-3), varnish B, and varnish R which were obtained by the said synthesis examples 1-6. The blended components were kneaded with three roll mills to obtain a photocurable thermosetting resin composition.

Performance rating:

<Dry Film Manufacturing>

PET film (Mitsubishi polyester) so that the film thickness after drying the photocurable and thermosetting resin composition which has thermosetting by alkali development type of the said Examples 1-12 and Comparative Examples 1-10 using an applicator, respectively may be 30 micrometers Co., Ltd. R310: 16 µm), and dried at 40 to 100 ℃ to obtain a dry film.

Substrate Manufacturing

After buffing the circuit-formed FR-4 substrate, the film prepared by the above method was subjected to 0.8 MPa, 80 ° C., 1 minute, and 133.3 Pa using a vacuum laminating machine (MVLP-500 manufactured by Meisei Seisakusho). It heated and laminated and obtained the evaluation board | substrate.

(1) solder heat resistance

Using each said evaluation board | substrate, the step tablet of Kodak N0.2 was set, and the exposure amount used as 6 steps was calculated | required. The negative exposure pattern in which the soldering resist pattern was drawn was applied to each said evaluation board | substrate, the exposure amount of the said result was investigated, and it developed and patterned using the developer of spray pressure of 0.2 MPa using the 1 mass% sodium carbonate aqueous solution of 30 degreeC. Then, it thermosetted 150 degreeC and 60 minutes, and obtained the cured coating film.

The rosin flux was apply | coated to this cured coating film, it immersed in 260 degreeC solder tank for 30 second, and the state of the cured coating film was evaluated based on the following references | standards.

○: the cured coating film does not have swelling, peeling or discoloration

(Triangle | delta): A thing with a little expansion, peeling, and discoloration in a cured coating film

X: A thing with swelling, peeling, and discoloration in a cured coating film

(2) electroless gold plating resistance

After exposure and development similar to the above, it thermosetted and manufactured the evaluation board | substrate. Each evaluation board | substrate was immersed in 30 degreeC acidic degreasing liquid (20 vol% aqueous solution of Metex L-5B by Nippon McDermid) for 3 minutes, and it was immersed for 3 minutes in water, and then washed with water. This evaluation substrate was immersed in 14.3 weight% ammonium persulfate aqueous solution for 3 minutes at room temperature, soft-etched, and then immersed in flowing water for 3 minutes, and water-washed. The test substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute, and then immersed in running water for 30 seconds to 1 minute and washed with water. This evaluation board | substrate was immersed in 30 degreeC catalyst liquid (Meltex Corporation make, 10 vol% aqueous solution of the metal plate activator 350) for 7 minutes, and the catalyst was impregnated, and it was immersed in flowing water for 3 minutes, and washed with water. The evaluation substrate provided with the catalyst was immersed in 85 degreeC nickel plating solution (20 vol% aqueous solution of Mel-Plate Ni-865M, pH 4.6) for 20 minutes, and electroless nickel plating was performed. The substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute, and then immersed in running water for 30 seconds to 1 minute and washed with water. Subsequently, the test substrate was immersed in a 95 ° C gold plating solution (manufactured by Meltex, Inc., an aqueous solution of 15% by weight of Aurololes UP and 3 vol% of potassium cyanide, pH 6) for 10 minutes to conduct electroless gold plating. It was immersed in water for 3 minutes in water, washed with water, and immersed in hot water at 60 ° C. for 3 minutes, and washed with water. After sufficiently washing with water, water was removed and dried to obtain an evaluation substrate on which electroless gold plating was performed. Thus, the peeling test by the cellophane adhesive tape was done using the board | substrate which performed electroless gold plating, and peeling and discoloration of a coating film were evaluated based on the following criteria.

○: no change at all

(Triangle | delta): A coating film peels only a little or discoloration is confirmed

X: Peeling was confirmed by the coating film

(3) HAST resistance

After exposure and development similarly to the above, it thermosetted and manufactured the evaluation board | substrate. This evaluation board | substrate was put into 121 degreeC, 2 atmospheres, and the high pressure high temperature high humidity tank of 100% of humidity for 168 hours, and the state change of the cured coating film was evaluated. It evaluated by the following evaluation criteria.

○: no peeling, discoloration and dissolution

△: any of peeling, discoloration and elution

X: peeling, discoloration, and elution are seen a lot.

(5) Insulation after HAST test

In the same manner to the above, the photocurable thermosetting resin composition was printed on the whole surface of the FR-4 substrate on which the comb-shaped electrode (line / space = 50 micrometers / 50 micrometers) was formed, and the exposure was performed. After development, it was thermally cured to prepare an evaluation substrate. This evaluation board | substrate was put into the high temperature, high humidity tank in the atmosphere of 130 degreeC and 85% of humidity, the voltage 5V was charged, and the HAST test was performed for 168 hours. Electrical insulation after the HAST test was measured.

○: 1010 Ω or more

Δ: 1010 to 108 Ω

×: 108 Ω

(6) evaluation of warpage

In the same manner as described above, the photocurable thermosetting resin composition was printed on the entire surface of the FR-4 substrate having a substrate thickness of 60 micrometers, followed by exposure and development, followed by thermal curing to prepare an evaluation substrate. This evaluation board | substrate (400 mm x 300 mm) was made into the test piece, the four corners of the test piece were measured on the plane, and the sum total of the value was measured as the amount of deflection deformation.

○: 20 mm or less

△: 20 mm to 40 mm

×: 40 mm or more

As mentioned above, the result of having evaluated the photocurable thermosetting resin composition of Examples 1-12 and Comparative Examples 1-10 is shown to the following Tables 4-6.

As is apparent from Tables 4 to 6, the photocurable and thermosetting resin composition of the present invention is excellent in solder heat resistance, electroless gold plating resistance, PCT resistance, and insulation after HAST testing required for solder resists and package substrate resists. In addition, even when using a thin plate used for package substrates such as QFP, BGA, CSP, it was found that less warpage.

On the other hand, Comparative Examples 1, 5, and 8 using the general-purpose carboxyl group-containing photosensitive resin and the carboxyl group-containing urethane (meth) acrylate compound (B) had large warpage, and were also poor in PCT resistance and insulation after the HAST test.

Further, Comparative Examples 2, 4, 6, and 9 using only the carboxyl group-containing photosensitive resins (A-1, A-2, A-3) of the present invention have large warpage and are used for package substrates such as QFP, BGA, and CSP. It turned out that it could not be used for the thin substrate which becomes.

Moreover, the comparative examples 3, 7, and 10 which used only the carboxyl group-containing urethane (meth) acrylate compound (B) were inferior to solder heat resistance.

Since the photocurable and thermosetting resin composition of this invention uses together the carboxyl group-containing photosensitive resin which is excellent in heat resistance and chemical-resistance, and the carboxyl group-containing urethane (meth) acrylate compound which is excellent in flexibility and film forming property, it is photocurable and alkali developability. To package substrates such as QFP, BGA, and CSP that require excellent insulation reliability such as excellent heat resistance, water resistance, electroless plating resistance, chemical resistance, electrical insulation, flexible resistance, and PCT resistance, as well as excellent adhesion to substrates and substrates. Can be used.

Moreover, since the photocurable and thermosetting resin composition of this invention can provide a board | substrate with little hardening shrinkage and a curvature, it can also respond to TAB, T-BGA, T-CSP, and UT-CSP.

Claims (13)

(A-1) Epoxy compound (a) which has two or more epoxy groups in 1 molecule, Compound (b) which has one reactor which reacts with one or more alcoholic hydroxyl groups and epoxy groups other than this alcoholic hydroxyl group in 1 molecule, Carboxyl group-containing photosensitive resin obtained by making polybasic acid anhydride (d) react with reaction product with unsaturated group containing monocarboxylic acid (c), (A-2) A reaction product obtained by reacting a compound (e) having two or more phenolic hydroxyl groups in one molecule with an alkylene oxide (f) or a cyclocarbonate compound (g) and an unsaturated group-containing monocarboxylic acid carboxyl group-containing photosensitive resin obtained by making polybasic acid anhydride (d) react with the reaction product with (c), and (A-3) Linear polyfunctional epoxy compound (h) obtained by alternating polymerization of a bifunctional epoxy compound and a compound having two reactors capable of reacting with an epoxy group, and reacting epihalohydrin with the resulting hydroxyl group Carboxyl group-containing photosensitive resin obtained by making polybasic acid anhydride (d) react with reaction product with unsaturated group containing monocarboxylic acid (c).  Any one or two or more of (B) carboxyl group-containing urethane (meth) acrylate compound, (C) photoinitiator, (D) a thermosetting component having two or more cyclic ether groups and / or cyclic thioether groups in one molecule, and (E) thinner Photocurable thermosetting resin composition characterized by including the. The compound (b) according to claim 1, wherein in the carboxyl group-containing photosensitive resin (A-1), a compound (b) having at least one alcoholic hydroxyl group in one molecule and one reactor reacting with an epoxy group other than the alcoholic hydroxyl group is contained in one molecule. It is a compound which has one or more alcoholic hydroxyl groups and one carboxyl group, The photocurable thermosetting resin composition characterized by the above-mentioned. The compound (b) according to claim 1, wherein in the carboxyl group-containing photosensitive resin (A-1), a compound (b) having at least one alcoholic hydroxyl group in one molecule and one reactor reacting with an epoxy group other than the alcoholic hydroxyl group is contained in one molecule. It is a phenolic compound which has one or more alcoholic hydroxyl groups, The photocurable thermosetting resin composition characterized by the above-mentioned. 2. The linear polyfunctional epoxy compound (h) according to claim 1, wherein the linear polyfunctional epoxy compound (h) reacts with a difunctional aromatic epoxy compound, a difunctional phenol compound and / or an aromatic dicarboxylic acid. It is a polyfunctional epoxy compound obtained, The photocurable thermosetting resin composition characterized by the above-mentioned. The said carboxyl group-containing urethane (meth) acrylate compound (B) is a hydroxyl-group containing (meth) acrylate compound (i), a dimethylol alkanoic acid (j), and a diiso cyanate compound (k). It is a compound obtained by making it react, and its acid value is 30-100 mgKOH / g, The photocurable thermosetting resin composition characterized by the above-mentioned. The carboxyl group-containing urethane (meth) acrylate compound (B) is a hydroxyl group-containing (meth) acrylate compound (i), dimethylol alkanoic acid (j), a diisocyanate compound (k) and a polymer. It is a compound obtained by making polyol (m) react, and its acid value is 30-100 mgKOH / g, The photocurable thermosetting resin composition characterized by the above-mentioned. The said dimethylol alkanoic acid (j) is any 1 or more types of dimethylol propionic acid and dimethylol butanoic acid, The photocurable thermosetting resin composition of Claim 5 characterized by the above-mentioned. The compounding ratio of the said carboxyl group-containing photosensitive resin (any 1 type, or 2 or more types of A-1, A-2, A-3) and the said carboxyl group-containing urethane (meth) acrylate compound (B) is It is a ratio of 85: 15-15: 85, The photocurable thermosetting resin composition characterized by the above-mentioned. The compounding quantity of the said photoinitiator (C) is 0.01-30 mass parts with respect to 100 mass parts of total amounts of the said carboxyl group-containing photosensitive resin (A) and the said carboxyl group-containing urethane (meth) acrylate compound (B). The compounding amount of the thermosetting component (D) is 0.5 to 2.0 equivalents based on 1 equivalent of the total amount of the carboxyl groups of the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing urethane (meth) acrylate compound (B), The compounding quantity of a diluent (E) is 5-420 mass parts with respect to 100 mass parts of total amounts of the said carboxyl group-containing photosensitive resin (A) and the said carboxyl group-containing urethane (meth) acrylate compound (B), The photocurable and thermosetting property characterized by the above-mentioned. Resin composition. (F) Curing catalyst is further contained, The compounding quantity is 0.1-20 mass parts with respect to 100 mass parts of all resin compositions, The photocurable thermosetting resin composition of Claim 1 characterized by the above-mentioned. The dry film obtained by apply | coating the photocurable and thermosetting resin composition of any one of Claims 1-10 on a carrier film, and drying it. Hardened | cured material obtained by hardening | curing the photocurable thermosetting resin composition of any one of Claims 1-10, or the dry film of Claim 11 by active energy ray irradiation and heating. A printed wiring board in which a solder resist film as a permanent protective film is formed on a circuit board having a patterned conductor layer, wherein the solder resist film is the photocurable or thermosetting resin composition according to any one of claims 1 to 10, or The cured film of the dry film of Claim 11 is included, The printed wiring board characterized by the above-mentioned.