JP2001278952A - Photo-setting, thermosetting composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid photo-setting, thermosetting composition capable of an alkali development that can respond to a high density and a face packaging of a printed wiring board and also with which the hardening film is obtained in the excellent characteristics such as a heat resistance, an adhesion, a definition, an electroless deposition resistance and an electrical characteristic, etc., required of a solder resist and a layer insulation, etc., and such as a hygroscopicity resistance and a PCT resistance, etc., especially required of an IC package. SOLUTION: The photo-setting, thermosetting composition capable of an alkali development which contains the active energy ray hardening resin which is obtained by reacting the reaction product of (A) (a) an amine compound containing two or more of amino groups in a molecular and the compound (b) shown by formula (1), (B) with a polybasic acid anhydride, and a photopolymerization initiator and as an essential component, the thermosetting component made of the epoxy compound having two or more epoxy groups is provided, furthermore it can contain (D) a photosensitivity (meth)acrylate and/or (E) an organic solvent (In the formula, R1 or R2 shows a hydrogen atom or a methyl group, independently to each other).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkali-developable photo-curable and thermo-curable composition.
Suitable for use as a permanent mask for printed wiring boards or interlayer insulating layers of multilayer wiring boards. After irradiation with ultraviolet rays, develop an image with a dilute alkaline aqueous solution to form an image. Heat treatment after active energy ray irradiation, or heat treatment Finish hardening by a subsequent active energy ray irradiation step or heat treatment to achieve excellent heat resistance, adhesion, electroless plating resistance, electrical properties, resolution, moisture absorption resistance, and PCT (pressure cooker) resistance. The present invention relates to a liquid alkali-developable photocurable / thermosetting composition capable of forming a film.

[0002]

2. Description of the Related Art At present, solder resists of some commercial printed wiring boards and most of industrial printed wiring boards are formed by irradiating ultraviolet rays and developing them from the viewpoint of high precision and high density. A liquid development type solder resist that is finally cured (finally cured) by heat and light irradiation is used. In consideration of environmental problems, a liquid solder resist of an alkali developing type using a dilute aqueous alkali solution as a developing solution has become mainstream. For example, JP-A-61-243869 discloses an alkali developing type solder resist using a diluted alkaline aqueous solution, in which an acid anhydride is added to a reaction product of a novolak type epoxy compound and an unsaturated monobasic acid. A solder resist composition comprising a photosensitive resin, a photopolymerization initiator, a diluent and an epoxy compound, is disclosed in Japanese Patent Application Laid-Open No. Hei 3-253093, which discloses a reaction product of a novolak type epoxy compound and an unsaturated monobasic acid. A solder resist composition comprising a photosensitive resin to which an acid anhydride is added, a photopolymerization initiator, a diluent, vinyl triazine or a mixture of vinyl triazine and dicyandiamide and a melamine resin is disclosed.
No. 1137, Japanese Unexamined Patent Publication No. 3-250012,
There is disclosed a solder resist composition comprising an epoxy resin which is a reaction product of salicylaldehyde, a monohydric phenol and epichlorohydrin, a photopolymerization initiator, an organic solvent, and the like.

[0003]

As described above, several material systems have been proposed as solder resists, and they are currently used in large quantities in actual production of printed wiring boards. However, in response to the increase in the density of printed wiring boards accompanying the recent reduction in the size and weight of electronic devices, solder resists are also required to have higher performance. More recently, QFP (Quad Flat Pack Package) and SOP (Small Outline Package) using lead frame and sealing resin
An IC package using a printed wiring board provided with a solder resist and a sealing resin has appeared in place of an IC package referred to as a so-called IC package. In these new packages, metal such as ball-shaped solder is arranged in an area on one side of the printed wiring board with solder resist, and the IC chip is directly connected to the other side by wire bonding or bumps, and the sealing resin is used. It has a sealed structure, and is called by a name such as BGA (ball grid array) and CSP (chip scale package). These packages have more pins and are easier to miniaturize than packages of the same size such as QFP. Also, in mounting, a low defect rate is realized by the self-alignment effect of the ball-shaped solder, and the introduction thereof is being rapidly promoted.

However, conventionally, printed wiring boards on which a commercially available alkali-developing solder resist is applied have been inferior in PCT resistance, which is a long-term reliability test of the package, and peeling of the solder resist film has occurred. In addition, the so-called popcorn phenomenon, which causes cracks in the solder resist film inside the package and its surroundings due to the moisture absorbed inside the package during reflow during package mounting due to the moisture absorption of the solder resist, has been regarded as a problem.
Such problems of moisture absorption resistance and long-term reliability are not limited to the above-described mounting technology, but include solder resists of general printed wiring boards and interlayer insulating layers of multilayer wiring boards such as build-up boards. It is also undesirable in products for other uses.

Accordingly, an object of the present invention is to provide heat resistance, adhesion, resolution, electroless plating resistance, electric resistance required for conventional solder resists of printed wiring boards and interlayer insulating layers of multilayer wiring boards. A cured film that maintains or improves the characteristics such as the characteristics and has excellent characteristics such as moisture absorption resistance and PCT (pressure cooker) resistance required especially for IC packages is obtained. It is an object of the present invention to provide a liquid photo-curable / thermo-curable composition which can cope with the development and is alkali developable.

[0006]

In order to achieve the above object, according to the present invention, there are provided (A) (a) an amine compound having two or more amino groups in one molecule; (C) an active energy ray-curable resin obtained by reacting a reaction product of the compound represented by the formula (1) with a polybasic acid anhydride, (B) a photopolymerization initiator, and (C) one molecule An alkali-developable photo-curable / thermo-curable composition characterized by containing, as an essential component, a thermosetting component comprising an epoxy compound having two or more epoxy groups therein. The photocurable and thermosetting composition of the present invention can further contain (D) a photosensitive (meth) acrylate compound and / or (E) an organic solvent.

Embedded image (In the formula, R ¹ and R ² independently represent a hydrogen atom or a methyl group.)

In a preferred embodiment, the thermosetting component (C) contains (C-1) an epoxy compound having two or more epoxy groups in one molecule and (C-2) an epoxy curing agent. . The mixing ratio of each component is not limited to a specific ratio, but the photopolymerization initiator (B) is added in an amount of 0.5 to 30 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin (A). Part, epoxy compound (C-
1) 10 to 100 parts by mass, and if necessary, 0.1 to 20 parts by mass of the epoxy curing catalyst (C-2), 0 to 60 parts by mass of the photosensitive (meth) methacrylate compound (D),
It is desirable to use the organic solvent (E) in a ratio of 10 to 500 parts by mass.

In a preferred embodiment of the method for forming a cured film from the alkali-developable photo-curable and thermo-curable composition, the composition is applied to a substrate, for example, a surface of a printed wiring board on which a circuit is formed. Apply by screen printing, roll coating, curtain coating, spray coating, etc., dry in a far infrared drying oven or hot air drying oven, etc., and then directly irradiate active energy rays such as laser light according to the pattern, Alternatively, irradiate active energy rays from a high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, electrodeless lamp, etc. through a patterned photomask, selectively expose according to a predetermined exposure pattern, and develop unexposed parts with an alkaline aqueous solution. To form a pattern, then heat treatment after irradiation with active energy rays, or after heat treatment Curing that is obtained by performing an active energy irradiation step or finish curing by heat treatment, and has excellent properties such as heat resistance, adhesion, electroless plating resistance, electrical properties, resolution, moisture absorption resistance, and PCT resistance. A coating (solder resist coating) is provided.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The alkali-developable liquid photocurable / thermosetting composition of the present invention comprises, as an active energy ray-curable resin (A), (a) two or more amino acids per molecule. An amine compound having a group, and (b) the general formula (1)
And (c) an active energy ray-curable resin obtained by reacting a polybasic acid anhydride with a reaction product of the compound represented by the formula (1).

That is, the active energy ray-curable resin (A) is obtained by adding an unsaturated group represented by the general formula (1) to the amino group of the amine compound (a) having two or more amino groups in one molecule. The epoxy group of the contained compound (b) is reacted, the product becomes photo-curable by the radical polymerizable unsaturated bond, and the amino group and / or secondary amine of the obtained unsaturated ester compound is obtained. And / or by reacting the polybasic anhydride (c) with the alcoholic hydroxyl group generated in the above reaction, a carboxyl group is introduced and becomes soluble in an aqueous alkali solution,
Alkaline developability is obtained. The reaction of the above-mentioned unsaturated ester compound with the polybasic acid anhydride (c) is mainly carried out by a secondary amine or an amino group (the amino group of the amine compound (a) is replaced by an unsaturated group represented by the general formula (1)). (In the case where the amino group remains due to partial reaction of the epoxy group of the containing compound (b)), which means that the heat resistance and the P value are lower than in the case of the reaction for the alcoholic hydroxyl group.
It is preferable in terms of CT resistance. When an amino group remains and the polybasic acid anhydride (c) reacts with the amino group to introduce an imide bond, an effect of improving chemical resistance can be obtained. In the active energy ray-curable resin (A) thus obtained, the reaction between the carboxyl group and the epoxy compound (C) proceeds sufficiently at a predetermined temperature by heat treatment. As a result, the cured film becomes excellent in moisture absorption resistance and PCT resistance, and cured film characteristics such as heat resistance, adhesion, and plating resistance such as electroless plating resistance are improved.

Due to the above-described effects, the use of the photo-curable and thermo-curable composition of the present invention makes it possible to improve the BG of printed wiring boards.
Even in an IC package such as A or CSP, the solder resist film is not peeled or cracked, and can be mounted with high reliability. In addition, even when exposed to high temperature or high humidity conditions, the cured film does not crack or peel off from the base material, and has excellent properties as described above. It can be advantageously used for applications such as an interlayer insulating layer of a multilayer wiring board.

Hereinafter, each component of the photocurable and thermosetting composition of the present invention will be described in detail. First, the active energy ray-curable resin (A) used in the present invention is a carboxyl group-containing photosensitive resin as described above. Such a carboxyl group-containing photosensitive resin (A) has
160 mgKOH / g, preferably 30 to 120 mgK
It is desirable to have an acid number in the range of OH / g.
The acid value of the carboxyl group-containing photosensitive resin is 20 mg KOH
If it is lower than / g, the solubility in an aqueous alkali solution becomes poor, and it becomes difficult to develop the formed coating film. on the other hand,
If it is higher than 160 mgKOH / g, the surface of the exposed portion is developed irrespective of the exposure conditions, which is not preferable.

The amine compound (a) having two or more amino groups in one molecule includes, for example, an aromatic polyamine (d) represented by the following general formula (2).

Embedded image (In the formula, A represents a phenylene group, an alkyl-substituted phenylene group, a diphenylene group, a diphenylether group, or a naphthenyl group, and R ³ represents a halogen atom, a hydroxyl group, a lower alkoxyl group having 4 or less carbon atoms or a lower alkyl group having 5 or less carbon atoms. And R ³ may be the same or different, and may form a ring.
Is an integer of 0 to 300, k is 1 or 2, and p is an integer of 0 to 3. )

The aromatic polyamine (d) is, for example,
The aromatic amine compound is used in an amount of about 1.0 to 10.3 per 1 mol of the bishalogenomethyl derivative represented by the following general formula (3).
It can be added in a range of 0 mol and can be obtained by a two-step reaction.

Embedded image (In the formula, A represents a phenylene group, an alkyl-substituted phenylene group, a diphenylene group, a diphenyl ether group, or a naphthenyl group, and X represents a halogen atom.)

As the aromatic amine compound, a compound represented by the following general formula (4) can be suitably used.

Embedded image (Wherein, R ³ represents a halogen atom, a hydroxyl group, a lower alkoxyl group having 4 or less carbon atoms or a lower alkyl group having 5 or less carbon atoms, and R ³ may be the same or different, and K is 1 or 2, and p is an integer of 0 to 3.) As one of such aromatic polyamines (d), "anilics" from Mitsui Chemicals, Inc. What is marketed under the trade name of A-15 "can also be used for the present invention.

Another example of the amine compound (a) having two or more amino groups in one molecule is an aromatic polyamine (e) represented by the following general formula (5).

Embedded image Aromatic polyamine (e) represented by the above general formula (5)
Is obtained, for example, by neutralizing an aniline derivative with hydrochloric acid to form a solution of an aniline derivative hydrochloride, and reacting the aniline derivative with formaldehyde so that formaldehyde is about 0.25 to 1.0 mol per 1 mol of the aniline derivative. be able to. Examples of the aniline derivative include aniline, p- (m- or o-) chloroaniline, p- (m-
Or o-) toluidine, p- (m- or o-) ethylaniline, p- (m- or o-) isopropylaniline,
p- (m- or o-) n-propylaniline, p- (m
-Or o-) Methoxyaniline or the like can be used alone or in combination of two or more. Poly (phenylenemethylene) polyamine obtained by the reaction between aniline and formaldehyde is also industrially produced as a raw material for polyurethane. For example, MDA-220,
MDA-150 (all manufactured by Mitsui Chemicals, Inc.) can be directly used as the aromatic polyamine compound in the present invention.

The amino group of the amine compound (a) having two or more amino groups in one molecule is represented by the general formula (1) having an epoxy group and a radical polymerizable unsaturated bond in one molecule. By reacting the compound (b), an unsaturated ester compound can be easily obtained.
Examples of the compound (b) represented by the general formula (1) include glycidyl methacrylate, glycidyl acrylate, 2-methyl glycidyl methacrylate, 2-methyl glycidyl acrylate, and the like. These may be used alone or in combination of two or more. Can be used. When the aromatic polyamine (d) or the aromatic polyamine (e) is subjected to a ring-opening addition reaction with the compound (b) to obtain an unsaturated ester compound, for example, the aromatic polyamine (d) or the aromatic polyamine (d) Polyamine (e)
The compound (b) is blended in an amount of about 0.2 to 2.3 equivalents, preferably 0.3 to 1.5 equivalents, relative to 1 equivalent of a hydrogen atom directly bonded to a nitrogen atom contained therein. In a solvent or without a solvent, about 30 to 150 ° C, preferably 50 to 13 ° C.
The reaction is carried out at 0 ° C. and preferably in the presence of air. In order to prevent gelation due to polymerization during the reaction, it is preferable to use known and commonly used polymerization inhibitors such as hydroquinones such as methylhydroquinone and hydroquinone; and benzoquinones such as p-benzoquinone and p-toluquinone.

In order to reduce the reaction time, a ring-opening addition catalyst can be used. As the ring-opening addition catalyst,
For example, water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; phenol;
phenols such as t-butylcatechol; salicylic acid,
Organic acids such as citric acid and malic acid; and boron trifluoride-monoethanolamine complex. As the inert solvent, for example, toluene, xylene, dimethylformamide and the like can be used, but a catalyst itself such as ethyl alcohol and acetic acid can also be used as a reaction medium.

The active energy ray-curable resin (A) of the present invention comprises a polybasic acid anhydride (c) in which the unsaturated ester compound produced by the above reaction is substituted with an amino group and / or a secondary amine and / or an alcoholic hydroxyl group. The reaction is carried out in the presence or absence of an organic solvent described below, in the presence of a polymerization inhibitor such as hydroquinone or oxygen,
Usually, it is carried out at about 50 to 130 ° C. At this time, if necessary, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride,
An imidazole compound such as 2-ethyl-4-methylimidazole and a phosphorus compound such as triphenylphosphine may be added as a catalyst.

The polybasic acid anhydride (c) includes methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydroanhydride. Alicyclic dibasic anhydrides such as phthalic acid, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride Aliphatic or aromatic dibasic acid anhydrides such as acid and trimellitic anhydride; or biphenyltetracarboxylic dianhydride, diphenylethertetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride Anhydrous, anhydrous pyromerit , Benzophenone aliphatic such as tetracarboxylic dianhydrides or aromatic tetracarboxylic acid dianhydride and the like, can be used one or two or more of these. Of these, alicyclic dibasic acid anhydrides are particularly preferred.

Examples of the photopolymerization initiator (B) include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone. Acetophenones such as 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoamino group propanone-1,2-benzyl Amino group acetophenones such as -2-dimethylamino group 1- (4-morpholinophenyl) -butan-1-one, N, N-dimethylamino group acetophenone;
Methylanthraquinone, 2-ethylanthraquinone, 2
Anthraquinones such as -t-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; acetophenone dimethyl ketal, benzyl Ketals such as dimethyl ketal; organic peroxides such as benzoyl peroxide and cumene peroxide; 2,4,5-triarylimidazole dimer, riboflavin tetrabutyrate, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole , 2-
Thiol compounds such as mercaptobenzothiazole; 2,
Organic halogen compounds such as 4,6-tris-s-triazine, 2,2,2-tribromoethanol and tribromomethylphenylsulfone; benzophenones such as benzophenone and 4,4'-bisdiethylamino group benzophenone or xanthones; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.
These known and commonly used photopolymerization initiators can be used alone or as a mixture of two or more. Further, N, N-dimethylamino group benzoic acid ethyl ester, N, N-dimethylamino group benzoic acid isoamyl ester, pentyl- Photoinitiating aids such as tertiary amines such as 4-dimethylamino benzoate, triethylamine and triethanolamine can be added. CG with absorption in the visible light region
A titanocene compound such as I-784 (manufactured by Ciba Specialty Chemicals) can also be added to promote the photoreaction. Particularly preferred photopolymerization initiator,
2-methyl-1- [4- (methylthio) phenyl] -2
-Morpholinoamino group propanone-1,2-benzyl-
2-dimethylamino group 1- (4-morpholinophenyl)
-Butan-1-one and the like, but not particularly limited thereto, as long as it absorbs light in the ultraviolet or visible light region and radically polymerizes an unsaturated group such as a (meth) acryloyl group. The photoinitiator and photoinitiator can be used alone or in combination. The amount of use is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin (A) (the same hereinafter as solid content).

Specific examples of the epoxy compound (C-1) as the thermosetting component (C) include Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, and Dainippon Ink manufactured by Yuka Shell Epoxy. Epicron 840, Epicron 850, manufactured by Chemical Industry Co., Ltd.
Epicron 1050, Epicron 2055, Epototos YD-011, YD-013, YD-1 manufactured by Toto Kasei Co., Ltd.
27, YD-128, D.C. E. FIG. R.
317, D.E. E. FIG. R. 331; E. FIG. R. 661,
D. E. FIG. R. 664, Araldide 6071, Araldide 608 manufactured by Ciba Specialty Chemicals
4, Araldide GY250, Araldide GY26
0, Sumi-Epoxy ESA-01 manufactured by Sumitomo Chemical Co., Ltd.
1, ESA-014, ELA-115, ELA-12
8. A.K. E. FIG. R. 330, A.I. E. FIG.
R. 331, A.I. E. FIG. R. 661, A.I. E. FIG. R. 664
(Both trade names) bisphenol A type epoxy resin; Epicoat YL903 manufactured by Yuka Shell Epoxy Co., Ltd.
Epicron 152 and Epicron 165 manufactured by Dainippon Ink and Chemicals, Epototo YDB-40 manufactured by Toto Kasei
0, YDB-500, D.C. E. FIG. R.
542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., A.D. E. FIG. R. 711, A.I. E. FIG. R. Brominated epoxy resins such as 714 (all trade names); Epicoat 152 and Epicoat 154 manufactured by Yuka Shell Epoxy, and D.C. E. FIG. N. 431; E. FIG. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, manufactured by Dainippon Ink and Chemicals, Epotohto YDCN-701, YDCN-704, manufactured by Toto Kasei Co., Ltd.
Araldide ECN1235, Araldide ECN1273, Araldide ECN1299, Araldide XPY307 manufactured by Ciba Specialty Chemicals,
Nippon Kayaku's EPPN-201, EOCN-102
5, EOCN-1020, EOCN-104S, RE-
306, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESCN-
195X, ESCN-220, A.C.
E. FIG. R. Novolak-type epoxy resins such as ECN-235 and ECN-299 (all of which are trade names); Epicron 830 manufactured by Dainippon Ink and Chemicals, Epicoat 807 manufactured by Yuka Shell Epoxy, Epototo YDF-1 manufactured by Toto Kasei
70, YDF-175, YDF-2004, Araldide XPY3 manufactured by Ciba Specialty Chemicals
Bisphenol F type epoxy resin such as 06 (all trade names); Epototo ST-2004, ST manufactured by Toto Kasei Co., Ltd.
-Hydrogenated bisphenol A type epoxy resin such as -2007, ST-3000 (trade name); Epicoat 604 manufactured by Yuka Shell Epoxy Co., Ltd., Epototo YH-4 manufactured by Toto Kasei Co., Ltd.
Glycidylamine-type epoxy resin such as Araldide MY720 manufactured by Ciba Specialty Chemicals, Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (all trade names); Araldide manufactured by Ciba Specialty Chemicals Hydantoin type epoxy resins such as CY-350 (trade name); alicyclic epoxy resins such as Celloxide 2021 manufactured by Daicel Chemical Industries, Inc., and Araldide CY175 and CY179 manufactured by Ciba Specialty Chemicals; YL-933 manufactured by Yuka Shell Epoxy Co., Ltd .; E. FIG.
N. , EPPN-501, EPPN-502, etc. (all are trade names); trihydroxyphenylmethane type epoxy resin; YL-6056, YX-, manufactured by Yuka Shell Epoxy Co., Ltd.
Bixylenol type or biphenol type epoxy resin such as 4000 or YL-6121 (all trade names) or a mixture thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., Dainippon Bisphenol S type epoxy resin such as EXA-1514 (trade name) manufactured by Ink Chemical Industry; Bisphenol A novolak type epoxy resin such as Epicoat 157S (trade name) manufactured by Yuka Shell Epoxy; Tetraphenylolethane type epoxy resin such as Epicoat YL-931, Araldide 163 (all trade names) manufactured by Ciba Specialty Chemicals; Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical (All trade names) heterocyclic epoxy resin; Japan Diglycidyl phthalate resin, such as manufactured by Blemmer DGT fat Corporation; manufactured by Tohto Kasei Co., Ltd. ZX-1
A tetraglycidyl xylenoylethane resin such as 063;
Nippon Steel Chemical's ESN-190 and ESN-360, Dainippon Ink and Chemicals' HP-4032 and EXA-475
Naphthalene group-containing epoxy resin such as EXA-4700, HP-7200, HP-200 manufactured by Dainippon Ink and Chemicals, Inc.
Epoxy resin having a dicyclopentadiene skeleton such as 7200H; CP-50S, CP-50 manufactured by NOF Corporation
Glycidyl methacrylate copolymer-based epoxy resin such as M; furthermore, a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate;
It is not limited to these. These epoxy resins can be used alone or in combination of two or more.

The epoxy compound as described above is cured by heat to improve the properties of the solder resist such as adhesion and heat resistance. The compounding amount is 10 parts by mass or more and 100 parts by mass or less based on 100 parts by mass of the active energy ray-curable resin (A), and is preferably 20 to 100 parts by mass.
The ratio is 80 parts by mass. When the compounding amount of the epoxy compound (C-1) is less than 10 parts by mass, the moisture absorption of the cured film is increased, and the PCT resistance is easily lowered, and the solder heat resistance and the electroless plating resistance are also easily lowered. . On the other hand, 100
If the amount is more than 10 parts by mass, the developability of the coating film and the electroless plating resistance of the cured film will be poor, and the PCT resistance will also be poor.

Examples of the epoxy curing catalyst (C-2) include imidazole, 2-methylimidazole,
2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole and the like Dicyandiamide, benzyldimethylamine, 4- (dimethylamino group) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-
Amine compounds such as N, N-dimethylbenzylamine; hydrazine compounds such as adipic hydrazide and sebacic hydrazide; phosphorus compounds such as triphenylphosphine; and commercially available products such as those manufactured by Shikoku Chemicals Co., Ltd. 2MZ-A, 2MZ-OK, 2PHZ, 2P
4BHZ, 2P4MHZ (all are trade names of imidazole compounds), U-CAT3503 manufactured by San Apro
X, U-CAT3502X (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, D
BN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof).
In particular, the present invention is not limited to these, and may be any curing catalyst for an epoxy resin or one that promotes the reaction between an epoxy group and a carboxyl group, and may be used alone or as a mixture of two or more. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino group 6-methacryloyloxyethyl-S-triazine, 2-vinyl- which also functions as an adhesion promoter
2,4-diamino group S-triazine, 2-vinyl-4,
S-triazine derivatives such as 6-diamino group S-triazine / isocyanuric acid adduct and 2,4-diamino group 6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used. A compound that also functions as an imparting agent is used in combination with the curing catalyst. The compounding amount of the above-mentioned curing catalyst is sufficient in a usual quantitative ratio, for example, 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin (A). 0.0 parts by mass.

The photo-curable / thermo-curable composition of the present invention can contain a photosensitive (meth) acrylate compound (D) for the purpose of increasing the photoreactivity of the composition. As the photosensitive (meth) acrylate compound (D), a liquid, solid or semi-solid photosensitive (meth) acrylate compound having at least one (meth) acryloyl group in one molecule at room temperature can be used. The photosensitive (meth) acrylate compound which is liquid at room temperature serves to enhance the photoreactivity of the composition, adjusts the composition to a viscosity suitable for various coating methods, and assists solubility in an alkaline aqueous solution. Also fulfills. However, when a large amount of a photosensitive (meth) acrylate compound that is liquid at room temperature is used, the coating film cannot be dried to the touch, and the properties of the coating film tend to be deteriorated. Not preferred. The compounding amount of the photosensitive (meth) acrylate compound (D) is preferably from 0 to 60 parts by mass based on 100 parts by mass of the active energy ray-curable resin (A).

Examples of the photosensitive (meth) acrylate compound (D) include hydroxyl-containing acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate; polyethylene Water-soluble acrylates such as glycol diacrylate and polypropylene glycol diacrylate; polyfunctional polyester acrylates of polyfunctional alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate; trimethylolpropane, hydrogenated Ethylene oxide of polyfunctional alcohols such as bisphenol A or polyfunctional phenols such as bisphenol A and biphenol Acrylates of side adducts and propylene oxide adducts; polyfunctional or monofunctional polyurethane acrylates which are isocyanate modified products of the above-mentioned hydroxyl group-containing acrylates; bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or phenol novolak epoxy resin ( Epoxy acrylates which are (meth) acrylic acid adducts;
And methacrylates corresponding to the above acrylates, and these can be used alone or in combination of two or more. Among these, a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule is preferable.

The photo-curable and thermo-curable composition of the present invention dissolves the active energy ray-curable resin (A) and the photosensitive (meth) acrylate compound (D), and coats the composition. An organic solvent can be blended to adjust the viscosity to a method suitable for the method. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, and propylene glycol. Glycol ethers such as monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate;
Acetates such as butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; ethanol, propanol, ethylene glycol,
Alcohols such as propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha,
And petroleum solvents such as hydrogenated petroleum naphtha and solvent naphtha. These organic solvents can be used alone or as a mixture of two or more. The compounding amount of the organic solvent can be any amount according to the application method, but is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin.

The photo-curable and thermo-curable compositions of the present invention include:
Further, if necessary, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica,
Known or customary inorganic fillers such as crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica can be used alone or in combination of two or more.
These are used for the purpose of suppressing curing shrinkage of the coating film and improving properties such as adhesion and hardness. The compounding amount of the inorganic filler is 100 parts of the active energy ray-curable resin (A).
10 to 300 parts by mass, preferably 30 to 20 parts by mass
A proportion of 0 parts by weight is suitable.

The composition of the present invention may further comprise, if necessary, a known and commonly used coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black and naphthalene black; ,
Known and commonly used thermal polymerization inhibitors such as hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, and phenothiazine; known and commonly used thickeners such as finely divided silica, organic bentonite, and montmorillonite; silicone-based, fluorine-based, and polymer-based Known and commonly used additives such as a foaming agent and / or a leveling agent, a silane coupling agent such as an imidazole type, a thiazole type, and a triazole type can be blended.

The photo-curable / thermo-curable composition of the present invention containing the above-mentioned components is diluted as necessary to adjust the viscosity to be suitable for a coating method. By applying a screen printing method, a curtain coating method, a play coating method, a roll coating method, etc. to the printed wiring board, for example, by volatilizing and drying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. And a tack-free coating film can be formed. After that, the resist pattern can be formed by selectively exposing with an active energy ray through a photomask on which a pattern is formed, and developing the unexposed portion with a dilute alkaline aqueous solution to form a resist pattern. Irradiation of active energy rays or final curing (final curing) only by heat curing, adhesion, hardness, solder heat resistance, chemical resistance, solvent resistance, electrical insulation, electrolytic corrosion resistance, resolution A cured film (solder resist film) having excellent plating resistance, PCT resistance, and moisture absorption resistance is formed.

As the alkaline aqueous solution, an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used. Further, as an irradiation light source for photocuring, 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, or the like is appropriate. In addition, a laser beam or the like can be used as the active energy ray.

[0032]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but it is needless to say that the present invention is not limited to the following examples. Note that “parts” and “%” are based on mass unless otherwise specified.

Synthesis Example 1 267 parts of Anilix A-15 (manufactured by Mitsui Chemicals, Inc., amination 0.64 equivalent / 100 g) was placed in a reaction vessel equipped with a thermometer, a reflux condenser, an air blowing pipe, and a stirrer. Charge and raise the temperature to 60 ° C. in an air atmosphere to dissolve. Thereafter, the temperature is raised to 80 ° C. with stirring, and the temperature is maintained. Next, 243 parts of glycidyl methacrylate and 0.3 part of methylhydroquinone are sequentially charged and reacted at 80 ° C. for about 9 hours. The reaction is tracked by the amount of unreacted glycidyl methacrylate by gas chromatography, and the end point is a reaction rate of 95% or more. After that, carbitol acetate 30
0 parts and 189 parts of tetrahydrophthalic anhydride were sequentially charged, and the temperature was raised to 80 ° C., and the reaction was carried out for about 5 hours. The reaction was measured by measuring the acid value and the total acid value of the reaction solution by potentiometric titration, followed by the obtained addition rate.
% Is defined as the end point. The carboxyl group-containing photosensitive resin thus obtained has an acid value of a solid of 100 mg KO.
H / g. Hereinafter, this reaction solution is referred to as A-1 varnish.

Synthesis Example 2 317 parts of Anilix A-15 (manufactured by Mitsui Chemicals, Inc., aminated 0.64 equivalents / 100 g) was placed in a reaction vessel equipped with a thermometer, a reflux condenser, an air blowing pipe, and a stirrer. Charge and raise the temperature to 60 ° C. in an air atmosphere to dissolve. Thereafter, the temperature is raised to 80 ° C. with stirring, and the temperature is maintained. Next, 288 parts of glycidyl methacrylate and 0.3 part of methylhydroquinone are sequentially charged and reacted at 80 ° C. for about 9 hours. The reaction is tracked by the amount of unreacted glycidyl methacrylate by gas chromatography, and the end point is a reaction rate of 95% or more. After that, carbitol acetate 30
0 parts and 95 parts of tetrahydrophthalic anhydride were sequentially charged,
The temperature was raised to 80 ° C., and the reaction was carried out for about 5 hours. The reaction was measured by measuring the acid value and the total acid value of the reaction solution by potentiometric titration, followed by the obtained addition rate, and the reaction rate was 95%.
The above is the end point. The carboxyl group-containing photosensitive resin thus obtained has an acid value of 50 mg KOH /
g. Hereinafter, this reaction solution is referred to as A-2 varnish.

Synthesis Example 3 A polymethylene polyaniline MDA-150 represented by the following formula (6) (manufactured by Mitsui Chemicals, Inc., containing an amino group) was placed in a reaction vessel equipped with a thermometer, a reflux condenser, an air blowing pipe, and a stirrer. (Amount: 15.8%) 212 parts are charged, and the temperature is raised to 60 ° C. in an air atmosphere to dissolve. Then, with stirring 80
Heat to ℃ and maintain the temperature.

Embedded image (However, the average value of n is 0.8) Next, 298 parts of glycidyl methacrylate and 0.3 part of methylhydroquinone are sequentially charged and reacted at 80 ° C. for about 9 hours. The reaction was monitored by the amount of unreacted glycidyl methacrylate by gas chromatography, and the reaction rate was 95%.
The above is the end point. Then, carbitol acetate 3
00 parts and 190 parts of tetrahydrophthalic anhydride were sequentially charged, and the temperature was raised to 80 ° C., and the reaction was carried out for about 5 hours. The reaction was measured by measuring the acid value and the total acid value of the reaction solution by potentiometric titration, followed by the obtained addition rate.
% Is defined as the end point. The carboxyl group-containing photosensitive resin thus obtained has an acid value of a solid of 100 mg KO.
H / g. Hereinafter, this reaction solution is referred to as A-3 varnish.

Synthesis Example 4 A polymethylene polyaniline MDA-150 represented by the above formula (6) (manufactured by Mitsui Chemicals, Inc., containing an amino group) was placed in a reaction vessel equipped with a thermometer, a reflux condenser, an air blowing pipe, and a stirrer. (Amount: 15.8%) 251 parts were charged, and the temperature was increased to 60 ° C. in an air atmosphere to dissolve. Then, with stirring 80
Heat to ℃ and maintain the temperature. Next, 354 parts of glycidyl methacrylate and 0.3 part of methylhydroquinone are sequentially charged and reacted at 80 ° C. for about 9 hours. The reaction is tracked by the amount of unreacted glycidyl methacrylate by gas chromatography, and the end point is a reaction rate of 95% or more. Thereafter, 300 parts of carbitol acetate and 95 parts of tetrahydrophthalic anhydride were sequentially charged, and the temperature was raised to 80 ° C., and the reaction was carried out for about 5 hours. In the reaction, the acid value and the total acid value of the reaction solution are measured by potentiometric titration, followed by the obtained addition rate, and the end point is a reaction rate of 95% or more. The carboxyl group-containing photosensitive resin thus obtained had a solid acid value of 50 mgKOH / g. Less than,
This reaction solution is called A-4 varnish.

Comparative Synthesis Example 1 Cresol novolak type epoxy resin (Epiclon N-
695, manufactured by Dainippon Ink and Chemicals, epoxy equivalent 220)
367 parts were placed in a reaction vessel equipped with a thermometer, a reflux cooler, and a stirrer, and 300 parts of carbitol acetate was added, followed by heating and melting. Next, 0.46 parts of hydroquinone and 1.38 parts of triphenylphosphine were added. The mixture was heated to 95 to 105 ° C., and 143 parts of methacrylic acid was gradually dropped, and the mixture was reacted for 16 hours. This reaction product is
After cooling to 0 to 90 ° C, tetrahydrophthalic anhydride 19
0 parts were added and reacted for 8 hours. The carboxyl group-containing photosensitive resin thus obtained has an acid value of 10
It was 0 mgKOH / g. Hereinafter, this reaction solution is referred to as B-
Called one varnish.

Comparative Synthesis Example 2 Cresol novolak type epoxy resin (Epiclon N-
695, manufactured by Dainippon Ink and Chemicals, epoxy equivalent 220)
435 parts were placed in a reaction vessel equipped with a thermometer, a reflux condenser, and a stirrer, and 300 parts of carbitol acetate was added thereto, followed by heating and melting. Next, 0.46 parts of hydroquinone and 1.38 parts of triphenylphosphine were added. The mixture was heated to 95 to 105 ° C., 170 parts of methacrylic acid was gradually added dropwise, and reacted for 16 hours. This reaction product is
Cool to 0-90 ° C and add 95% tetrahydrophthalic anhydride.
Was added and the mixture was reacted for 8 hours. The thus obtained carboxyl group-containing photosensitive resin has an acid value of 50 m as a solid.
gKOH / g. Hereinafter, this reaction solution is referred to as B-2 varnish.

Comparative Synthesis Example 3 Phenol novolak type epoxy resin (EPPN-20)
1, 351 parts of Nippon Kayaku Co., Ltd., epoxy equivalent 190) was placed in a reaction vessel equipped with a thermometer, a reflux cooler, and a stirrer, and 300 parts of carbitol acetate was added and dissolved by heating.
Next, 0.46 parts of methylhydroquinone and 1.38 parts of triphenylphosphine were added. 95-
The mixture was heated to 105 ° C., and 159 parts of methacrylic acid was gradually dropped, and the mixture was reacted for 16 hours. The reaction product is
After cooling to 0 ° C., 190 parts of tetrahydrophthalic anhydride were added and reacted for 8 hours. The carboxyl group-containing photosensitive resin thus obtained has an acid value of 100 mg as a solid.
KOH / g. Hereinafter, this reaction solution is referred to as B-3 varnish.

Comparative Synthesis Example 4 Phenol novolak type epoxy resin (EPPN-20)
1, 417 parts of Nippon Kayaku Co., Ltd., epoxy equivalent 190) was placed in a reaction vessel equipped with a thermometer, a reflux condenser, and a stirrer, and 300 parts of carbitol acetate was added and dissolved by heating.
Next, 0.46 parts of methylhydroquinone and 1.38 parts of triphenylphosphine were added. 95-
The mixture was heated to 105 ° C., and 189 parts of methacrylic acid was gradually added dropwise, and reacted for 16 hours. The reaction product is
After cooling to 0 ° C., 94 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. The carboxyl group-containing photosensitive resin thus obtained has an acid value of 50 mg KO as a solid.
H / g. Hereinafter, this reaction solution is referred to as B-4 varnish.

Examples 1 to 4 and Comparative Examples 1 to 4 The components shown in Table 1 using the varnishes obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 to 4 were kneaded with a three-roll mill. Thus, a photo-curable / thermo-curable resin composition was obtained. Table 2 shows the characteristic values of each composition.

[Table 1]

[0042]

[Table 2] In addition, the method of the performance test in said Table 2 is as follows.

(1) Developability The compositions of the above Examples and Comparative Examples were patterned and formed.
Apply the whole surface by screen printing on the copper foil substrate
Dry for 40, 50, 60, or 70 minutes to room temperature
After cooling, 1% Na at 30 ° C_TwoCO_ThreeSpray aqueous solution
Pressure 2kg / cm ^TwoDevelop for 60 seconds under the conditions of
The presence or absence of the development residue of the coating film was visually confirmed. ：: Completely developed. Δ: Part of the coating film remains. X: The coating film remains completely.

Characteristic test: The compositions of the above Examples and Comparative Examples were applied to the entire surface of the patterned copper foil substrate by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature. A negative film is applied to this substrate, and the solder resist pattern is exposed under the condition of an exposure amount of 500 mJ / cm ² ,
1% Na ₂ CO ₃ aqueous solution at 30 ° C, spray pressure 2kg / c
Development was performed for 60 seconds under the conditions of m ² to obtain a resist pattern. This substrate is integrated in a UV conveyor furnace with an integrated exposure of 1
UV irradiation under the condition of 000 mJ / cm ² ,
Cured by heating at 60 ° C. for 60 minutes.

(2) Solder heat resistance The evaluation substrate coated with the rosin-based flux
After immersion in a solder bath set at ℃ and washing the flux with denatured alcohol, swelling and peeling of the resist layer were evaluated visually. The criteria are as follows. ：: No peeling was observed even when immersion was repeated 6 times or more for 10 seconds. Δ: When immersion is repeated 6 times or more for 10 seconds, the film is slightly peeled off. ×: The resist layer swelled and peeled within 6 times of immersion for 10 seconds.

(3) Adhesion The above evaluation substrate was cut in a grid pattern in accordance with the test method of JIS D0202, and a peel test was performed with a cellophane adhesive tape to evaluate the peeling of the resist layer. The criteria are as follows. ：: no peeling was observed at all △: slight peeling ×: peeling of the resist layer

(4) Electroless Plating Resistance Using a commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 0.5 μm and gold 0.03 μm, and the resist is removed by tape peeling. After evaluating the presence or absence of peeling of the layer and the presence or absence of plating soaking, the resist layer was peeled off by tape peeling after being immersed in a solder bath for 10 seconds, washed and dried under the above-mentioned (2) solder heat resistance test conditions. Was evaluated. The criteria are as follows. A: No change is observed even after solder immersion. ：: No change was observed after plating, but slight discoloration or peeling was observed after soldering. Δ: Slight peeling and soaking were observed after plating, and peeling after soldering was also observed. ×: Peeling occurs after plating.

(5) Electric Corrosion Resistance An evaluation substrate was prepared under the above conditions by using a comb electrode B coupon of IPC B-25 instead of the copper foil substrate, and a bias voltage of DC 100 V was applied to the comb electrode. , 85
° C, 85% R.C. H. The presence / absence of migration after 1,000 hours in the constant temperature / humidity bath was confirmed. The criteria are as follows. ：: no change observed at all △: slight change ×: migration occurred

(6) Insulation Characteristics An evaluation substrate was prepared under the above conditions using a comb electrode B coupon of IPC B-25 instead of a copper foil substrate, and a bias voltage of 500 V DC was applied to the comb electrode. The insulation resistance was measured.

(7) Line width reproducibility Line / space = 80 on negative film used for exposure
μm / 80μm pattern is formed in advance and solder
-Image on resist 500 mJ / cm ^TwoCondition
Baking in 1% Na at 30 ° C_TwoCO_ThreeSpray aqueous solution
Pressure 2kg / cm^TwoDevelopment for 60 seconds under the conditions
Was cured by heating at 150 ° C. for 60 minutes. Hardening
After that, measure the width of the surface line and the bottom line of the formed line
The difference was used as an evaluation of line width reproducibility.

(8) Water Absorption A cured solder resist film is formed on a ceramic substrate (alumina substrate) whose mass has been measured in advance under the above conditions, and the total mass is measured. Then, add this to 22 ° C. ion-exchanged water for 2 hours.
After immersion for 4 hours, the mass was measured, and the rate of increase in mass was defined as the water absorption.

(9) PCT resistance The printed wiring board on which the solder resist film was formed under the above conditions was used in a PCT device (TABAI ESPEC HAS).
121 using TSYSTEM TPC-412MD).
It processed for 168 hours on conditions of 2 degreeC of ° C, and evaluated the state of the cured film. ：: Peeling, discoloration and no elution. Δ: Any of peeling, discoloration and elution was observed. X: Many peeling, discoloration and elution are observed.

[0053]

As described above, according to the present invention, the heat resistance, adhesion, and resolution required for conventional solder resists for printed wiring boards and interlayer insulating layers for multilayer wiring boards are obtained.
Maintains or improves properties such as electroless plating resistance and electrical properties, and obtains a cured film with excellent properties such as moisture absorption resistance and PCT resistance required for IC packages. Provided is a liquid photocurable / thermosetting composition that can be applied to surface mounting and that can be alkali-developed. By using such a photocurable / thermosetting composition of the present invention, a printed wiring board is provided. BGA, CS
Even in an IC package such as P, peeling and cracking do not occur in the solder resist film, and highly reliable mounting is possible. In addition, even when exposed to high temperature or high humidity conditions, the cured film does not crack or peel off from the base material, and has excellent properties as described above. It can be advantageously used for applications such as an interlayer insulating layer of a multilayer wiring board.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shoji Minegishi No. 388, Okura Oaza, Arashiyama-cho, Hiki-gun, Saitama Prefecture Taiyo Ink Manufacturing Co., Ltd. (72) Tadashi Sanyu Okura 388, Arashiyama-cho, Hiki-gun, Saitama Ban Tai Ink Manufacturing Co., Ltd. Arashiyama Plant F-term (reference) 2H025 AA02 AA10 AA14 AB15 AC01 AD01 BC74 BC85 BC87 CC17 FA17 FA29 4J036 AA01 AD01 AF01 DB15 DB17 EA01 EA03 FB03 HA12 JA09

Claims (1)

[Claims] (A) (a) an amine compound having two or more amino groups in one molecule, and (b) an amine compound represented by the following general formula (1):
(C) an active energy ray-curable resin obtained by reacting a reaction product of a compound represented by
(B) a photopolymerization initiator, and (C) a thermosetting component comprising an epoxy compound having two or more epoxy groups in one molecule as essential components. Curable and thermosetting composition. Embedded image (In the formula, R ¹ and R ² independently represent a hydrogen atom or a methyl group.)