JP2000327742A - Photosetting/thermosetting composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject halogen-free composition with flame retardancy and self-extinguishability, generating no toxic gas such as dioxins when burned by including a resin compound prepared by reaction between a compound having epoxy groups and unsaturated monocarboxylic acid, etc., followed by reaction with a polybasic acid anhydride, a photopolymerization initiator, and diluent(s), etc. SOLUTION: This composition is obtained by including (A) a resin compound prepared by reaction of (i) a compound having at least two epoxy groups in one molecule (e.g. a phenol or cresol novolak epoxy resin) with (ii) an unsaturated monocarboxylic acid [e.g. (meth)acrylic acid] and (iii) a compound of the formula (R1 and R2 are each an aromatic ring or alkyl), e.g. diphenylphosphinic acid followed by reaction with (iv) a saturated or unsaturated polybasic acid anhydride (e.g. succinic anhydride), (B) a photopolymerization initiator, (C) a compound having at least two epoxy groups in one molecule, and (D) reactive and/or inert diluent(s).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a printed wiring board,
In particular, photo-curing is useful as an interlayer insulating material for multilayer printed wiring boards and a solder resist by the build-up method, etc.
It relates to a thermosetting composition.

[0002]

2. Description of the Related Art With the rapid progress of recent semiconductor parts,
Electronic devices tend to be smaller and lighter, have higher performance, and have more functions. Following these trends, the density of printed wiring boards has been increasing. For example, thinner conductor circuits and higher multilayers, smaller diameters such as through via holes and blind via holes, and high-density mounting by surface mounting of small chip components are being advanced. In response to these high-density printed wiring boards, demand for multilayer printed wiring boards has been increasing, and for this reason, new methods for manufacturing multilayer printed wiring boards such as a build-up method have been proposed. One of the properties uniformly required for these applications is flame retardancy or self-extinguishing. Conventionally, halogen-containing epoxy resins have been used as thermosetting components in order to impart flame retardancy or self-extinguishing properties.

[0003]

However, when a halogen-containing epoxy resin is used, a harmful gas such as dioxin is generated at the time of burning a multilayer printed wiring board after disposal. . Therefore, an object of the present invention is to provide a halogen-free photocurable / thermosetting composition having no flame retardant or self-extinguishing property without generating harmful gas such as dioxin during combustion. .

[0004]

According to the present invention, there is provided, according to the present invention, (A) a compound having two or more epoxy groups in one molecule; A resin compound obtained by reacting a carboxylic acid and (c) a compound represented by the following general formula (1) and then reacting with (d) a saturated or unsaturated polybasic acid anhydride; (B) a photopolymerization initiator , (C) a compound having two or more epoxy groups in one molecule, and (D) a flame-retardant or self-extinguishing photocuring characterized by comprising a reactive and / or non-reactive diluent. A thermosetting and thermosetting composition is provided.

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In a preferred embodiment, the compound (a) having two or more epoxy groups in one molecule used in the synthesis of the resin compound (A) is a phenol or cresol novolac type epoxy resin. In another preferred embodiment, the amount of the compound (c) represented by the general formula (1) is based on 1 equivalent of the epoxy group of the compound (a) having two or more epoxy groups in one molecule. ,
It is preferably 0.2 to 0.8 equivalent. If the amount is less than 0.2 equivalent, the effect of flame retardancy becomes small, which is not preferable. On the other hand, when it exceeds 0.8 equivalent, the content of unsaturated monocarboxylic acid becomes small, and it becomes difficult to obtain alkali developability of the photocured film, which is not preferable.

In another aspect, the resin compound (A) preferably has an acid value of 50 to 150 mgKOH / g. If the acid value is less than 50 mgKOH / g, it is difficult to obtain alkali developability, which is not preferable. On the other hand, when the acid value is larger than 150 mgKOH / g, it is difficult to obtain development resistance, which is not preferable. In still another preferred embodiment, the compound (c) represented by the general formula (1) used in the synthesis of the resin compound (A) includes:
Diphenylphosphinic acid is used.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The photocurable and thermosetting composition according to the present invention comprises (A) (a) a compound having two or more epoxy groups in one molecule, and (b) an unsaturated monocarboxylic acid. An acid and (c) a resin compound obtained by reacting a compound represented by the following general formula (1) and then reacting with (d) a saturated or unsaturated polybasic acid anhydride; (B) a photopolymerization initiator;
(C) a compound having two or more epoxy groups in one molecule, and (D) a reactive and / or non-reactive diluent. That is, a feature of the present invention is that a phosphorus compound having the following general formula (1), which is effective in flame retardancy or self-extinguishing properties, is converted into a carboxyl group-containing photosensitive resin compound (the components (a), (b) and ( d) The resin compound (A) introduced into the reaction product of the component) is used. As a result, a photo-curable / thermo-curable composition that is excellent in flame retardancy or self-extinguishing properties even in a halogen-free state can be formed.

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Compound (a) having two or more epoxy groups in one molecule used for the synthesis of resin compound (A)
Known epoxy resins, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, hydrogenated bisphenol A epoxy resin, biphenol epoxy resin, bixylenol epoxy resin, phenol novolak Epoxy resin, cresol novolak epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, glycidyl ether compound such as bisphenol A novolak epoxy resin, terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer Glycidyl ester compounds such as acid diglycidyl ester, triglycidyl isocyanurate, N, N, N ', N'-tetraglycidyl metaxylenediamine Glycidylamine compounds such as N, N, N ', N'-tetraglycidylbisaminomethylcyclohexane and N, N-diglycidylaniline are used alone or in combination of two or more. Phenol or cresol novolak type epoxy resin, which is easy to increase the sensitivity and adjust the phosphorus introduction rate, is exemplified.

The unsaturated monocarboxylic acid (b) used in the synthesis of the resin compound (A) includes (meth) acrylic acid, a mono (meth) acrylate obtained by adding a polybasic anhydride to a (meth) acrylate containing a hydroxyl group. 2-acryloyloxyethyl) succinic acid, mono (2-acryloyloxyethyl) phthalic acid, mono (2-acryloyloxyethyl)
Hexahydrophthalic acid, mono (2-acryloyloxypropyl) succinic acid, mono (2-acryloyloxypropyl) phthalic acid, mono (2-acryloyloxypropyl) hexahydrophthalic acid, mono (2-methacryloyloxyethyl) succinic acid Mono (2-methacryloyloxyethyl) phthalic acid, mono (2-methacryloyloxyethyl) hexahydrophthalic acid, mono (2-methacryloyloxypropyl) succinic acid, mono (2-methacryloyloxypropyl) phthalic acid, mono (2 -Methacryloyloxypropyl) hexahydrophthalic acid and the like, and are used alone or in combination of two or more.
In this specification, (meth) acrylic acid is a general term for acrylic acid, methacrylic acid, and mixtures thereof, and the same applies to other similar expressions.

The compound (c) represented by the general formula (1) used in the synthesis of the resin compound (A) includes:
Phosphinic acid derivatives such as dimethylphosphinic acid, dibutylphosphinic acid, and diphenylphosphinic acid are used, and more preferably, diphenylphosphinic acid having no toxicity and having good stability is used.

The saturated or unsaturated polybasic anhydride (d) used in the synthesis of the resin compound (A) includes phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, succinic acid, trimellitic acid, and pyromellitic acid. There are anhydrides such as acids, and among them, anhydrides of tetrahydrophthalic acid, hexahydrophthalic acid and succinic acid are particularly preferred from the viewpoint of the properties of the cured coating film. These saturated or unsaturated polybasic acid anhydrides (d) can be used alone or in combination of two or more.

Examples of the photopolymerization initiator (B) include various commonly used photopolymerization initiators, for example, benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; acetophenone, Acetophenones such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1-
Aminoacetophenones such as [4- (methylthio) phenyl] -2-morpholinoaminopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; 2-methylanthraquinone;
Anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone and 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-
Diethylthioxanthone, 2-chlorothioxanthone,
Thioxanthones such as 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; and xanthones. These known and commonly used photopolymerization initiators can be used alone or in combination of two or more. In addition, known or commonly used photosensitizers such as tertiary amines can be used alone or in combination of two or more. Can be used together. Mixing ratio of these photopolymerization initiators (the total amount when using a photosensitizer in combination)
Is suitably 1 to 30 parts by weight, preferably 5 to 25 parts by weight, per 100 parts by weight of the resin compound (A). If the amount of the photopolymerization initiator is less than the above range, the photocurability of the composition is poor, while if it is large, the photocurability in a thick film is poor due to absorption of the photopolymerization initiator itself, which is preferable. Absent.

As the compound (C), various known and common epoxy resins similar to the epoxy compound (a) used in the synthesis of the resin compound (A) can be used. Specific examples of the epoxy compound (C) include, for example, EBPS-200 manufactured by Nippon Kayaku Co., Ltd. and EP manufactured by Asahi Denka Kogyo Co., Ltd.
X-30, Epicron E manufactured by Dainippon Ink and Chemicals, Inc.
Bisphenol S type epoxy resin such as XA-1514;
Diglycidyl phthalate resin such as Blemmer DGT manufactured by NOF Corporation; TEPIC series manufactured by Nissan Chemical Co., Ltd.
Heterocyclic epoxy resin such as Araldite PT810 manufactured by Ciba-Geigy; YX-4 manufactured by Yuka Shell Epoxy Co., Ltd.
Diluents such as bixylenol type epoxy resins such as 000; biphenol type epoxy resins such as YL-6056 manufactured by Yuka Shell Epoxy Co .; and tetraglycidyl xylenoylethane resins such as ZX-1063 manufactured by Toto Kasei. Insoluble epoxy resin, Epicoat 1009, 1031 manufactured by Yuka Shell Epoxy Co., Ltd., Epicron N-3050, N-7050, N- manufactured by Dainippon Ink and Chemicals, Inc.
9050, AER-664, AER manufactured by Asahi Kasei Corporation
-667, AER-669, YD-0 manufactured by Toto Kasei Co., Ltd.
12, YD-014, YD-017, YD-020, Y
D-002, XAC-5005 manufactured by Ciba-Geigy, G
Bisphenol A type epoxy resins such as T-7004, 6484T, 6099, DER-642U and DER-673MF manufactured by Dow Chemical Company, EP-5400 and EP-5900 manufactured by Asahi Denka Kogyo; ST manufactured by Toto Kasei -2
004, ST-2007 and other hydrogenated bisphenol A type epoxy resins; manufactured by Toto Kasei Co., Ltd., YDF-2004, Y
Bisphenol F type epoxy resin such as DF-2007;
Nippon Kayaku Co., Ltd. EPPN-201, EOCN-10
3, EOCN-1020, EOCN-1025, ECN-278, ECN-292, ECN manufactured by Asahi Kasei Corporation
-299, ECN-1273, EC manufactured by Ciba-Geigy
N-1299, YDCN-220L manufactured by Toto Kasei Co., Ltd.
YDCN-220HH, YDCN-702, YDCN-
704, YDPN-601, YDPN-602, Epicron N-673, N-6 manufactured by Dainippon Ink and Chemicals, Inc.
Novolak type epoxy resins such as 80, N-695, N-770, N-775; EPX-80 manufactured by Asahi Denka Kogyo KK
01, EPX-8002, EPPX-8060, EPP
Novolak-type epoxy resin of bisphenol A such as X-8061, Epicron N-880 manufactured by Dainippon Ink and Chemicals, Inc .; EPX-49-60, E manufactured by Asahi Denka Kogyo KK
Chelate type epoxy resin such as PX-49-30; Glyoxal type epoxy resin such as YDG-414 manufactured by Toto Kasei; YH-1402, ST-11 manufactured by Toto Kasei
0, Yuka Shell Epoxy YL-931, YL-
Amino group-containing epoxy resins such as 933; rubber-modified epoxy resins such as Epicron TSR-601 manufactured by Dainippon Ink and Chemicals, EPX-84-2 and EPX-4061 manufactured by Asahi Denka Kogyo Co., Ltd .: Sanyo Kokusaku Pulp ( DCE-4
A dicyclopentadiene phenolic type epoxy resin such as 00; a silicone-modified epoxy resin such as X-1359 manufactured by Asahi Denka Kogyo KK; and an ε-caprolactone-modified epoxy such as Praxel G-402 and G-710 manufactured by Daicel Chemical Industries, Ltd. Epoxy resin soluble in diluents such as resin;
And the like.

These epoxy resins can be used alone or in combination of two or more. In particular, it is preferable to disperse them in the form of fine particles in the composition, and for that purpose, they are solid or semi-solid at room temperature. It is preferable to use a resin that does not dissolve in the resin compound (A) and the diluent (D) used during kneading, and / or has a solubility that does not adversely affect photosensitivity and developability. That is, it is preferable to use a fine-grained epoxy resin that is hardly soluble in the diluent, or a combination of a hardly soluble epoxy resin and a soluble epoxy resin. At this time, the amount of the epoxy resin soluble in the diluent is preferably less than 50 mol% of the epoxy equivalent of all epoxy compounds as thermosetting components. When the blending ratio of the epoxy resin soluble in the diluent is 50 mol% or more (the blending ratio of the hardly soluble epoxy resin in the diluent is less than 50 mol%), the touch drying property after the preliminary drying and the development life decrease. This is not preferred. When a large amount of an epoxy resin soluble in a diluent is used in combination, the viscosity increases slightly before application to a printed wiring board. It is desirable that the two-component curing agent containing (C) as a main component be used and that the two components be mixed for use.

The preferred range of the amount of the epoxy compound (C) used is such that the epoxy group of the compound (C) is 0.6-2. 0 equivalent, more preferably 1.0 to 1.6.
This is the equivalent ratio. If the amount of the epoxy group exceeds 2.0 equivalents, the developability of the unexposed portion of the coating film with an aqueous alkali solution and the characteristics of the coating film are undesirably deteriorated. On the other hand, if it is less than 0.6 equivalent, the crosslink density of the cured coating film decreases,
It is not preferable because required characteristics such as heat resistance cannot be obtained.

Representative examples of the reactive diluent used as the reactive and / or non-reactive diluent (D) include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; Mono- or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; acrylamides such as N, N-dimethylacrylamide and N-methylolacrylamide; aminos such as N, N-dimethylaminoethyl acrylate Alkyl acrylates; polyhydric alcohols such as hexadiol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like Polyvalent acrylates of adducts or adducts of propylene oxide ethylene oxide; phenoxy acrylate, bisphenol A
Acrylates such as diacrylates and ethylene oxide adducts of these phenols; acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; and melamine acrylate; and / or There are methacrylates corresponding to acrylates. The reactive diluents described above can be used alone or in combination of two or more. The preferred range of the amount of the reactive diluent used is 0 to 30 parts by weight per 100 parts by weight of the resin compound (A). When the mixing ratio of the reactive diluent exceeds the above range,
It is not preferable because the dryness to the touch of the coating film is reduced.

On the other hand, typical examples of the non-reactive diluent used as the reactive and / or non-reactive diluent (D) include ketones such as ethyl methyl ketone and cyclohexanone; toluene, xylene, tetra Aromatic hydrocarbons such as methylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether Glycol ethers such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene Recall monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, esters such as propylene carbonate; octane,
There are known and commonly used organic solvents such as aliphatic hydrocarbons such as decane; petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha. The non-reactive diluents as described above can be used alone or in combination of two or more. The preferred range of the amount of the non-reactive diluent used depends on the coating method, but is preferably 20 per 100 parts by weight of the resin compound (A).
３００300 parts by weight, preferably 30-200 parts by weight.

The photo-curable / thermo-curable composition of the present invention may be used in combination with a known and commonly used flame retardant in order to improve flame retardancy or self-extinguishing properties. For example, a melamine-phosphate; a phosphate compound; a polyphosphate compound; red phosphorus; an inorganic flame retardant such as aluminum hydroxide, magnesium hydroxide, zinc borate, a zirconium compound, or a molybdenum compound is used in combination. be able to. Further, phosphorus-containing compounds such as the resin compound (A) of the present invention include melamine, acetoguanamine, benzoguanamine,
When used in combination with a nitrogen-containing compound such as urea or dicyandiamide, flame retardancy or self-extinguishing properties can be improved. Further, a melamine resin, a benzoguanamine resin, a urea resin, a silicone resin, a phosphazene resin or the like, which is a thermosetting resin having flame retardancy, can be used in combination. These flame retardants and flame-retardant resins can be used in a range that does not deteriorate the properties of the coating film.

The photocurable / thermosetting composition of the present invention may be any of known materials such as barium sulfate, talc, silica, aluminum oxide and aluminum hydroxide for the purpose of improving the properties such as adhesion and hardness of the coating film. Conventional inorganic fillers can be used. The mixing ratio of these inorganic fillers is suitably not more than 100 parts by weight, preferably not more than 50 parts by weight, per 100 parts by weight of the resin compound (A). If the amount is more than the above range, the strength of the coating film is reduced, the sensitivity is lowered, and the like, which is not preferable. Further, if necessary, known and commonly used coloring pigments, coloring dyes, thermal polymerization inhibitors, thickeners, defoaming agents, leveling agents, coupling agents, flame retardant auxiliaries and the like can be used.
For the purpose of increasing the sensitivity, a phenothiazine-based, anthracene-based, coronene-based, benzanthracene-based, perylene-based, pyrene-based, merocyanine-based, ketocoumarin-based, or thioxanthone-based sensitizing dye can be added, if necessary. If necessary, imidazole salts, boron trifluoride complexes, organic metal salts, and the like can be added as latent curing catalysts. Further, for the purpose of preventing the oxidation of copper circuits, ie, copper oxidation, adenine, vinyl triazine, dicyandiamide, ortho tolyl biguanide,
Compounds such as melamine or salts thereof can be added. The compounding ratio of these compounds is 20 parts by weight or less per 100 parts by weight of the resin compound (A), and the addition of these compounds improves the chemical resistance of the cured coating film and the adhesion to the copper foil.

The photocurable and thermosetting composition of the present invention is applied to a printed wiring board on which a circuit is formed by a method such as a screen printing method, a curtain coating method, a spray coating method, and a roll coating method. By evaporating and drying (temporarily drying) the organic solvent contained in the composition at a temperature of 100 ° C., a coating film having excellent dryness to the touch and a long development life can be formed. Thereafter, it is selectively exposed to actinic rays through a photomask on which a pattern is formed, and an unexposed portion is developed with a dilute alkaline aqueous solution to form a resist pattern. By doing so, an insulating coating film having excellent adhesion, hardness, solder heat resistance, chemical resistance, solvent resistance, electrical insulation, and corrosion resistance is formed.

As the above-mentioned diluted alkaline aqueous solution, a diluted 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 suitable. In addition, a laser beam or the like can also be used as an active light beam for exposure.

[0022]

EXAMPLES The present invention will be specifically described below with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following, “parts” and “%” are all based on weight unless otherwise specified.

Synthesis Example 1 Cresol novolak type epoxy resin (Epiclon N-
680, manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent = 210) 210 parts were placed in a four-necked flask equipped with a stirrer and a reflux condenser, and 304 parts of carbitol acetate was added and dissolved by heating. Next, 2.0 parts of triphenylphosphine and diphenylphosphinic acid 1 were used as reaction catalysts.
09 parts were added and reacted at 90-100 ° C for 8 hours. Furthermore, after adding 0.1 part of hydroquinone as a polymerization inhibitor, 36 parts of acrylic acid was gradually dropped, and the mixture was reacted for 16 hours. The reaction was cooled to 80-90 ° C., and 101 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours.
After cooling, it was taken out. The photosensitive resin thus obtained contained 3.4% of phosphorus, had a nonvolatile content of 60%, and had an acid value of 82 mgKOH / g of solids. Hereinafter, this reaction solution is referred to as A varnish.

Comparative Synthesis Example 1 Cresol novolac type epoxy resin (Epiclon N-
695, manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent = 220) was placed in a four-necked flask equipped with a stirrer and a reflux condenser, and 214 parts of carbitol acetate was added and dissolved by heating. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of triphenylphosphine as a reaction catalyst were added. 95-105 ° C of this mixture
, And 72 parts of acrylic acid were gradually added dropwise, and reacted for 16 hours. The reaction is cooled to 80-90 ° C.
106 parts of tetrahydrophthalic anhydride were added, reacted for 8 hours, and taken out after cooling. The thus obtained photosensitive resin having both an ethylenically unsaturated bond and a carboxyl group has a nonvolatile content of 65% and an acid value of a solid of 100 mg.
KOH / g. Hereinafter, this reaction solution is referred to as B varnish.

Example 1 The following components (photocurable composition and thermosetting composition) using the A varnish obtained in Synthesis Example 1 were mixed with 3 parts each.
The mixture was kneaded with this roll mill to obtain a photocurable composition and a thermosetting composition. 60 parts of the photocurable composition and 16.5 parts of the thermosetting composition were mixed to obtain a photocurable / thermosetting composition. Photocurable composition A varnish 30 parts Irgacure 907 3 parts (Photopolymerization initiator manufactured by Ciba Specialty Chemicals Co., Ltd.) KS-66 0.5 part (Silicone defoamer manufactured by Shin-Etsu Chemical Co., Ltd.) Agent) phthalocyanine blue 0.2 part silica 21 parts talc 3.3 parts dipropylene glycol monomethyl ether 2 parts total 60 parts thermosetting composition triglycidyl isocyanurate 8.5 parts dipentaerythritol hexaacrylate 8 parts total 16.5 Department

Example 2 The following components (photocurable composition and thermosetting composition) using the A varnish obtained in Synthesis Example 1 were mixed with 3 parts each.
The mixture was kneaded with this roll mill to obtain a photocurable composition and a thermosetting composition. 60 parts of the photocurable composition and 18 parts of the thermosetting composition were mixed to obtain a photocurable / thermosetting composition. Photocurable composition A varnish 30 parts Irgacure 907 3 parts KS-66 0.5 part Phthalocyanine blue 0.2 parts Silica 21 parts Talc 3.3 parts Dipropylene glycol monomethyl ether 2 parts Total 60 parts Thermosetting composition Triglycidyl isocyanurate 8.5 parts Dipentaerythritol hexaacrylate 8 parts Melamine 1.5 parts Total 18 parts

Comparative Example 1 The following components (photocurable composition and thermosetting composition) using the B varnish obtained in Synthesis Example 2 were mixed with 3
The mixture was kneaded with this roll mill to obtain a photocurable composition and a thermosetting composition. 60 parts of the photocurable composition and 16.5 parts of the thermosetting composition were mixed to obtain a photocurable / thermosetting composition. Photocurable composition B varnish 30 parts Irgacure 907 3 parts KS-66 0.5 parts Phthalocyanine blue 0.2 parts Silica 21 parts Talc 3.3 parts Dipropylene glycol monomethyl ether 2 parts Total 60 parts Thermosetting composition Triglycidyl isocyanurate 8.5 parts Dipentaerythritol hexaacrylate 8 parts Total 16.5 parts

Comparative Example 2 The following components (photocurable composition and thermosetting composition) using the B varnish obtained in Synthesis Example 2 were mixed with 3
The mixture was kneaded with this roll mill to obtain a photocurable composition and a thermosetting composition. 60 parts of the photocurable composition and 18 parts of the thermosetting composition were mixed to obtain a photocurable / thermosetting composition. Photocurable composition B varnish 30 parts Irgacure 907 3 parts KS-66 0.5 parts Phthalocyanine blue 0.2 parts Silica 21 parts Talc 3.3 parts Dipropylene glycol monomethyl ether 2 parts Total 60 parts Thermosetting composition Triglycidyl isocyanurate 8.5 parts Dipentaerythritol hexaacrylate 8 parts Melamine 1.5 parts Total 18 parts

Comparative Example 3 The following components (photocurable composition and thermosetting composition) using the B varnish obtained in Synthesis Example 2 were mixed with 3
The mixture was kneaded with this roll mill to obtain a photocurable composition and a thermosetting composition. 60 parts of the photocurable composition and 40 parts of the thermosetting composition were mixed to obtain a photocurable / thermosetting composition. Photocurable composition B varnish 30 parts Irgacure 907 3 parts KS-66 0.5 parts Phthalocyanine blue 0.2 parts Silica 21 parts Talc 3.3 parts Dipropylene glycol monomethyl ether 2 parts Total 60 parts Thermosetting composition Brominated novolak type epoxy resin (Epoxy equivalent: 283, bromine content: 35.5%) 32 parts Dipentaerythritol hexaacrylate 8 parts Total 40 parts

Comparative Example 4 The following components (photocurable composition and thermosetting composition) using the B varnish obtained in Synthesis Example 2 were mixed with 3 parts each.
The mixture was kneaded with this roll mill to obtain a photocurable composition and a thermosetting composition. 60 parts of this photocurable composition and 42 parts of the thermosetting composition were mixed to obtain a photocurable / thermosetting composition. Photocurable composition B varnish 30 parts Irgacure 907 3 parts KS-66 0.5 parts Phthalocyanine blue 0.2 parts Silica 21 parts Talc 3.3 parts Dipropylene glycol monomethyl ether 2 parts Total 60 parts Thermosetting composition Brominated novolak type epoxy resin (epoxy equivalent: 283, bromine content: 35.5%) 32 parts Dipentaerythritol hexaacrylate 8 parts Melamine 2 parts Total 42 parts

Performance evaluation: The photo-curable and thermo-curable compositions obtained in each of the above Examples and Comparative Examples were applied to the entire surface of a substrate, dried at 80 ° C. for 20 minutes, and exposed through a photomask. And developed with an aqueous alkali solution. This substrate is
The composition was thermally cured at 60 ° C. for 60 minutes to produce an evaluation substrate.

(1) Solder heat resistance The substrate coated with the rosin-based flux was immersed in a solder bath set at 260 ° C. for 30 seconds, and the flux was washed with propylene glycol monomethyl ether acetate. Swelling, peeling and discoloration were evaluated. The criteria are as follows. : No change was observed at all △: Slight change was observed ×: The resist layer swelled and peeled

(2) Insulation Characteristics An evaluation board was prepared under the above conditions using a comb electrode B coupon of IPC B-25, and DC50 was applied to the comb electrode.
A bias of 0 V was applied, and the insulation resistance was measured.

(3) Self-extinguishing properties The photo-curable and thermo-curable compositions obtained in the above Examples and Comparative Examples were applied to the entire surface of a substrate, dried at 80 ° C. for 15 minutes, and then applied to the back surface. The entire surface was coated, dried at 80 ° C. for 20 minutes, exposed on both sides, and developed with an aqueous alkali solution. This substrate is thermally cured at 150 ° C. for 60 minutes, and the thickness of the cured coating film is about 80 μm.
m evaluation substrates were prepared. This substrate is 125 mm long,
The sample was cut to a width of 13 mm, the flame of a gas burner was brought into contact with the sample from below, and after holding for 10 seconds, the flame was kept away. Thereafter, the time during which the sample was burning was measured. Table 1 shows the obtained results.

[Table 1]

[0035]

As described above, self-extinguishing can be achieved by using the photocurable / thermosetting composition of the present invention as a solder resist for a printed wiring board or as an interlayer insulating material for a multilayer printed wiring board by a build-up method or the like. It is possible to obtain a cured product which has a property and does not generate toxic gas during combustion. Moreover, when a coating film comprising the photo-curable and thermo-curable composition of the present invention is formed on a printed wiring board, alkali development can be performed after exposure, and the exposed and cured portion is a solder resist excellent in self-extinguishing properties. Can be formed. Furthermore, it can be used for permanent protection resists related to printed wiring boards, photosensitive adhesives, paints, plastic reliefs, plastic hard coating agents, PS plates as offset printing plates, photosensitive liquids for screen printing, resist inks, etc. , Can be used in a wide range of fields.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tadahiro Sanyu No. 388, Okura, Arashiyama-cho, Hiki-gun, Saitama Prefecture Taiyo Ink Manufacturing Co., Ltd. Arashiyama Plant F-term (reference) 2H025 AA00 AB15 AC01 AD01 BC32 BC42 BC74 BC81 BC85 CA01 CC03 CC20 FA03 FA17 FA29 4J036 AA01 AA05 AF06 CA19 CA20 CA28 CB15 CC02 EA01 EA02 EA04 FA09 FA10 HA02 JA08 JA09 JA10

Claims (5)

[Claims] 1. A method comprising reacting (A) (a) a compound having two or more epoxy groups in one molecule with (b) an unsaturated monocarboxylic acid and (c) a compound represented by the following general formula (1). (B) a resin compound obtained by reacting a saturated or unsaturated polybasic acid anhydride, (B) a photopolymerization initiator,
A photocurable / thermosetting composition comprising (C) a compound having two or more epoxy groups in one molecule, and (D) a reactive and / or non-reactive diluent. Embedded image 2. After the resin compound (A) is reacted with an unsaturated monocarboxylic acid (b) and the compound (c) represented by the general formula (1) with a phenol or cresol novolak type epoxy resin, The composition according to claim 1, which is a resin compound obtained by reacting a saturated or unsaturated polybasic acid anhydride (d). 3. The resin compound (A) contains 2 per molecule.
The compound (c) represented by the general formula (1) is reacted with 0.2 to 0.8 equivalent to 1 equivalent of the epoxy group of the compound (a) having two or more epoxy groups, and then reacted with the epoxy residue. 2. A resin compound obtained by reacting an unsaturated monocarboxylic acid (b) and then reacting a saturated or unsaturated polybasic acid anhydride (d).
Or the composition according to 2. 4. The resin compound (A) has an acid value of 50 to 50.
2. The amount is 150 mgKOH / g.
The composition according to any one of claims 1 to 3. 5. The composition according to claim 1, wherein the compound (c) represented by the general formula (1) is diphenylphosphinic acid.