JP2001048955A - Flame retardant type energy beam photosensitive resin, photosensitive resin composition by using the same resin, and its cured material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin composition of which cured material is excellent in close adhering property, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance, flame retardant property, etc., excellent in developmental property and photosensitivity. SOLUTION: This flame resistant type energy beam photosensitive resin (B) is obtained by adding (d) a polybasic acid anhydride to (A) an epoxycarboxylate resin obtained by reacting (a) an epoxy compound having >=2 epoxy groups in a molecule with (b) an unsaturated group-containing monocarboxylic acid and (c) a phosphorus compound expressed by the formula (R1, R2 are each hydrogen atom, an alkyl group or an aryl group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel energy ray-sensitive resin, a composition and a cured product thereof, and more particularly to a resin suitable for a liquid solder resist which can be developed with an alkaline aqueous solution and is useful for manufacturing a printed circuit board.

[0002]

2. Description of the Related Art In the printed circuit board manufacturing industry, a solder resist is widely used as a permanent protective film for a printed circuit board. The solder resist is used for the purpose of preventing a solder bridge at the time of soldering, preventing corrosion of a conductor portion at the time of use, maintaining electrical insulation, and the like. Conventionally, a method of forming a solder resist by screen printing using a thermosetting ink or a photocurable ink has been widely used. However, when using this method, the accuracy of the obtained resist pattern is reduced due to bleeding, bleeding, sagging, and the like at the time of printing, and recent thinning, miniaturization, high density, and high function of printed circuit boards are performed. Is no longer available.

In order to cope with such a printed circuit board, many photo-curable liquid solder resists have been developed, and 50% or more are currently introduced. Among them, those which can be developed with an aqueous alkali solution have been attracting attention, and these compositions are essential components including a resin having a carboxyl group for dissolving in an aqueous alkaline solution and an ethylenically unsaturated group for imparting photocurability. It is characterized by doing. For example, JP-A-64-62375, JP-A-3-25
No. 3093, Japanese Patent Publication No. 1-54390, a phenolic or o-cresol novolak type epoxy resin is reacted with an unsaturated monobasic acid and further reacted with a saturated or unsaturated polybasic acid anhydride. A resist composition using the obtained resin is disclosed. JP-A-3-289656
JP-A-2-975 discloses a composition using a resin obtained by copolymerizing glycidyl (meth) acrylate or the like as a constituent and modifying an epoxy group in the same manner as the above-mentioned resin.
No. 13 discloses ethylene obtained by reacting a reaction product of an epoxy compound of a condensate of a phenol and an aromatic aldehyde having a phenolic hydroxyl group with (meth) acrylic acid with a polybasic carboxylic acid or an anhydride thereof. A composition using a polycarboxylic acid resin containing an unsaturated group is disclosed.

On the other hand, in recent years, personal injury due to fire accidents has increased, and safety measures for various industrial products have been promoted. Organic polymer materials are widely used in many electrical and electronic devices, including computers, and these materials are not only flammable, but are often poisoned by harmful gases generated during fires. Regulations on flame retardancy of materials against fire have become strict, and materials used for printed circuit boards and the like are no exception. In general, flame retardant
It is known to add compounds such as halogen-based compounds, antimony-based compounds, phosphorus-based compounds, and boron-based compounds, and inorganic fillers. However, it is known that halogen-based compounds and antimony-based compounds have a large burden on the environment, such as the generation of dioxins and toxicity during combustion.

[0005]

The flame retardancy is excellent, and the sensitivity, heat resistance, resolution, alkali aqueous solution developability, chemical resistance of the cured film, gold plating resistance, electrolytic corrosion resistance, PCT (pressure cooker test) It is desired to develop a flame-retardant energy ray photosensitive resin having excellent resistance and the like, a photosensitive resin composition using the same, and a cured product thereof.

[0006]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that an epoxy compound (a) having two or more epoxy groups in a molecule and an unsaturated group-containing monocarboxylic acid Flame-retardant energy obtained by adding a polybasic anhydride (d) to an epoxy carboxylate resin (A) obtained by reacting an acid (b) with a phosphorus compound (c) represented by the following formula (1) The radiation-sensitive resin (B) exhibits flame retardancy, and by using this flame-retardant energy ray-sensitive epoxy carboxylate resin (B), it exhibits high sensitivity and high resolution, and is easily alkali-developed. An energy ray-sensitive resin composition for printed circuit boards was obtained, and the cured film thereof was also excellent in flame retardancy, and was found to be excellent in solder heat resistance, chemical resistance, gold plating resistance, electrolytic corrosion resistance, and the like. completed. That is, the present invention provides (1) an epoxy compound (a) having two or more epoxy groups in a molecule, an unsaturated group-containing monocarboxylic acid (b), and the following formula (1)

[0007]

Embedded image

Wherein R ₁ and R ₂ are each a hydrogen atom,
Represents an alkyl group or an aryl group. A) a flame-retardant energy-ray-sensitive resin (B) obtained by adding a polybasic acid anhydride (d) to an epoxycarboxylate resin (A) obtained by reacting a phosphorus compound (c) 2) The flame-retardant energy ray-sensitive resin (B) according to (1), wherein the phosphorus content is 0.8 to 8% by weight, and (3) the phosphorus compound (c) is 9,8-dihydro- The flame-retardant energy ray-sensitive resin (B) according to any one of (1) and (2), which is 9-oxa-10-phosphaphenanthrene-10-oxide, (4) an epoxy compound (a) Is an epoxy compound (a) selected from a novolak type epoxy resin, a bisphenol type epoxy resin, a trisphenol methane type epoxy resin and a biphenol type epoxy resin, according to any one of (1) to (3). of The flame-retardant energy ray-sensitive epoxy carboxylate resin (B), (5) the unsaturated group-containing monocarboxylic acid (b) reacts (meth) acrylic acid, cinnamic acid, and maleic anhydride with an aminocarboxylic acid. The flame-retardant energy ray-sensitive epoxy carboxylate resin according to any one of (1) to (4), which is an unsaturated group-containing monocarboxylic acid (b) selected from the maleimide compounds obtained by the above method. B), (6) polybasic anhydride (d) is succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenetetrahydroanhydride Phthalic acid, dihydro-3-[(6-oxide-6H-dibenz [c, e] [1,2] oxaphospholin-6-yl) methyl ] The flame-retardant energy ray-sensitive resin (B) according to any one of (1) to (5), which is a polybasic anhydride selected from -2,5-furandione, (7) ) The solid content acid value of the flame-retardant energy ray-sensitive resin (B) is 50 to 150 mg · KOH / g.
The flame-retardant energy ray-sensitive resin (B) according to any one of (1) to (6), (8) and (1), wherein
To (7), comprising a flame-retardant energy ray-sensitive resin (B), a crosslinking agent (C), a photopolymerization initiator (D) and a curing component (E) according to any one of the above. The present invention provides a photosensitive resin composition, a cured product of the energy ray photosensitive resin composition described in (9) and (8), and a printed circuit board having a cured product layer described in (10) and (9). .

[0009]

DETAILED DESCRIPTION OF THE INVENTION The flame-retardant energy ray-sensitive resin (B) of the present invention comprises an epoxy compound (a) having two or more epoxy groups in a molecule and an unsaturated group-containing monocarboxylic acid (b). A resin obtained by adding a polybasic acid anhydride (d) to a reaction product of a compound represented by the formula (1) and a phosphorus compound (c). The content of phosphorus in this resin is preferably in the range of 0.8 to 8% by weight. When the amount is less than 0.8% by weight, the flame retardancy becomes insufficient, and when it exceeds 8% by weight, the addition amount of the unsaturated group-containing monocarboxylic acid (b) described later becomes relatively low. This is not preferred because the photosensitivity may be poor or the crosslinking density may be low.

The epoxy compound (a) having two or more epoxy groups in the molecule is not particularly limited, but is a novolak-type epoxy resin, a bisphenol-type epoxy resin, a trisphenol-type epoxy resin, which has improved heat resistance and good substrate adhesion. A methane type epoxy resin or a biphenol type epoxy resin is particularly preferable.

Examples of the phenol novolak type epoxy resin include Epiclon N-770 (manufactured by Dainippon Ink and Chemicals, Inc.); E. FIG. N438 (manufactured by Dow Chemical Company), Epicoat 154 (Yukaka Epoxy Co., Ltd.)
And RE-306 (manufactured by Nippon Kayaku Co., Ltd.). Examples of the cresol novolak type epoxy resin include Epicron N-695 (manufactured by Dainippon Ink and Chemicals, Inc.), EOCN-102S, and EOCN-103.
S, EOCN-104S (Nippon Kayaku Co., Ltd.), UVR
-6650 (manufactured by Union Carbide), ESCN-1
95 (manufactured by Sumitomo Chemical Co., Ltd.).

As the bisphenol type epoxy resin,
For example, Epicoat 828, Epicoat 1001 (manufactured by Yuka Shell Epoxy), UVR-6410 (manufactured by Union Carbide), D.C. E. FIG. Bisphenol A type epoxy resin such as R-331 (manufactured by Dow Chemical Company), YD-8125 (manufactured by Toto Kasei), bisphenol such as UVR-6490 (manufactured by Union Carbide), YDF-8170 (manufactured by Toto Kasei) An F-type epoxy resin or the like can be used.

Examples of the trisphenol methane type epoxy resin include TACTICX-742 (manufactured by Dow Chemical Company) and Epicoat E1032H60 (manufactured by Yuka Shell Epoxy Co., Ltd.). Examples of the biphenol-type epoxy resin include a bixylenol-type epoxy resin of YX-4000 (manufactured by Yuka Shell Epoxy) and YL-6121 (manufactured by Yuka Shell Epoxy).
And the like.

Examples of the unsaturated group-containing monocarboxylic acid (b) include maleimide compounds obtained by reacting (meth) acrylic acid, cinnamic acid, maleic anhydride and an aminocarboxylic acid such as aminocaproic acid. , (Meta)
Acrylic acid can be suitably used.

In the phosphorus compound (c) represented by the formula (1), for example, R1 and R2 each represent a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group,
Compounds which are alkyl groups such as n-butyl group, sec-butyl group and tert-butyl group, or aryl groups such as phenyl group, tolyl group, naphthyl group and the like, among which 9,8-dihydro- 9-oxa-10
-Phosphaphenanthrene-10-oxide is particularly preferred.

As a method for producing the epoxy carboxylate resin (A), for example, an epoxy compound (a) having two or more epoxy groups in a molecule, an unsaturated group-containing monocarboxylic acid (b) and a compound represented by the formula (1) , The epoxy compound (a) having two or more epoxy groups in the molecule and the unsaturated group-containing monocarboxylic acid (b) are first reacted, and then the formula (1) Reaction of the phosphorus compound (c) of
There is a method in which an epoxy compound (a) having two or more epoxy groups is first reacted with a phosphorus compound (c) of the formula (1), and then an unsaturated group-containing monocarboxylic acid (b) is reacted. Of these methods, the method is particularly preferable because the thermal polymerization of the unsaturated group-containing monocarboxylic acid (b) is suppressed and there is no possibility of gelation during the reaction.

The method of the present invention will be described in detail below. First, an epoxy compound (a) having two or more epoxy groups in a molecule and a phosphorus compound (c) of the formula (1) are prepared according to the present invention. A phosphorus-containing epoxy resin is obtained by reacting a calculated amount such that the phosphorus content in the flame-retardant energy ray photosensitive resin (B) is 0.8 to 8% by weight. At this time, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst is 0.1 to 10% by weight based on the reaction raw material mixture. The reaction temperature at that time is 100 to 200 ° C., and the reaction time is preferably 1 to 10 hours.
Examples of the catalyst used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide,
Triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, zirconium octoate and the like. As a method for obtaining this phosphorus-containing epoxy resin, for example, JP-A-11-166
035 publication.

Next, the unsaturated group-containing monocarboxylic acid (b) is preferably used in an amount of 0.5 to 1.5 equivalents, particularly preferably 0.1 to 1.5 equivalents, per equivalent of the epoxy group of the obtained phosphorus-containing epoxy resin. 7 to 1.1 equivalents are reacted to obtain a phosphorus-containing epoxy carboxylate resin (A). It is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is 0.1 to 10% by weight based on the reaction raw material mixture.
It is. At that time, the reaction temperature is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. As a catalyst used in this reaction, for example, triethylamine,
Benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide,
Examples include benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, zirconium octoate and the like.

The flame-retardant energy ray-sensitive resin (B) of the present invention can be obtained by ring-opening addition of a polybasic acid anhydride (d) to a phosphorus-containing epoxy carboxylate resin (A). In this reaction, 0.1 to 1.0 equivalent of a polybasic acid anhydride is reacted per 1 equivalent of the hydroxyl group with respect to the alcoholic hydroxyl group in the phosphorus-containing epoxy carboxylate resin. Exceeding this amount is not preferred because gelation or the like may occur during the reaction, or plating resistance or solvent resistance may be impaired. The reaction temperature is 60 to 150.
C is preferable, and the reaction time is about 1 to 10 hours. The acid value of the flame-retardant energy-ray-sensitive resin (B) thus obtained is preferably from 50 to 150 mg · KOH / g, particularly preferably from 40 to 140 mg · KOH / g. Examples of the polybasic anhydride (d) include, for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, Dihydro-3-[(6-oxide-
6H-dibenz [c, e] [1,2] oxaphospholin-6-yl) methyl] -2,5-furandione.

The photosensitive resin composition of the present invention contains a flame-retardant energy ray photosensitive resin (B), a crosslinking agent (C), a photopolymerization initiator (D) and a curing component (E). The term "photosensitivity" as used herein refers to a property of being polymerized and cured in the presence or absence of a photopolymerization initiator (D) by irradiation with an energy beam such as an electron beam or ultraviolet light. The amount of the flame-retardant energy ray-sensitive resin (B) contained in the photosensitive resin composition is from 30 to 30 parts by weight based on 100 parts by weight of the solid content of the composition.
It is preferably 90 parts by weight, particularly preferably 40 to 80 parts by weight.

As the crosslinking agent (C) used in the photosensitive resin composition of the present invention, for example, a crosslinking agent such as a (meth) acrylate compound, an azide compound, a diazo compound and a nitro compound can be used in combination. A (meth) acrylate compound, which can be radically polymerized by a photopolymerization initiator (D) described later and can easily undergo a crosslinking reaction with the flame-retardant energy-ray-sensitive resin (B), is particularly preferable. Examples of the (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, acryloyl monophorin, isobornyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and nonanediol di. (Meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Examples include acrylates such as pentaerythritol tetraacrylate, ditrimethylolpropanetetra (meth) acrylate, and dipentaerythritol poly (meth) acrylate. These can be used alone or in combination.

The amount of the crosslinking agent (C) used in the photosensitive resin composition of the present invention is preferably from 1 to 40% by weight when the total solid content of the photosensitive resin composition is 100% by weight. Particularly preferably, it is 5 to 30% by weight.

The photopolymerization initiator (D) used in the photosensitive resin composition of the present invention includes, for example, acetophenone,
2,2-diethoxy-2-phenylacetophenone, p
-Dimethylaminopropiophenone, dichloroacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Benzophenones such as acetophenones such as phenyl) -butanone-1, benzophenone, p-chlorobenzophenone, p, p-bisdimethylaminobenzophenone, p, p-bisdiethylaminobenzophenone, and 4-benzoyl-4'-methyl-diphenylsulfide Benzoin ethers such as benzyl, benzoin, benzoin methyl ether and benzoin isobutyl ether; ketals such as benzyl dimethyl ketal; thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone and 2-iso Thioxanthones such as propylthioxanthone, anthraquinone, 2,4,5-triarylimidazole dimer, 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide And the like. These photopolymerization initiators (D) can be used alone or
More than one species can be used in combination. The amount used is preferably 1 to 30% by weight, particularly preferably 2 to 20% by weight in the composition.

These photopolymerization initiators (D) are N, N-
Dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, N, N-dimethylaminobenzoic acid pentyl ester, 4,4′-bis (N, N-dimethylamino) -benzophenone, 4,
It can be used in combination with a sensitizer such as 4'-bis (N, N-dimethylamino) -benzophenone.
The use amount of the sensitizer is preferably 50% by weight or less based on the photopolymerization initiator (D).

The hardening component (E) used in the present invention comprises:
During the heat curing after development, it reacts with the carboxyl group in the unsaturated group-containing polycarboxylic acid resin (B) by heat to impart alkali resistance, solvent resistance, heat resistance, and electrical insulation to the cured coating film. is there. For these curing components (E), it is possible to use, for example, an epoxy resin which can enhance the resolution of the transfer pattern, has good development adhesion, and can enhance the gold plating resistance of the cured film.

Examples of these epoxy resins include phenol novolak type epoxy resin, cresol novolak type epoxy resin, trisphenolmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin. Resin, biphenol type epoxy resin,
Bisphenol-A type novolak type epoxy resin, naphthalene skeleton-containing epoxy resin, heterocyclic epoxy resin, and epoxy obtained by reacting these epoxy resins with 9,8-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Resins and the like can be mentioned.

Examples of the phenol novolak type epoxy resin include Epiclon N-770 (manufactured by Dainippon Ink and Chemicals, Inc.); E. FIG. N438 (manufactured by Dow Chemical Company), Epicoat 154 (Yukaka Epoxy Co., Ltd.)
And RE-306 (manufactured by Nippon Kayaku Co., Ltd.). Examples of the cresol novolak type epoxy resin include Epicron N-695 (manufactured by Dainippon Ink and Chemicals, Inc.), EOCN-102S, and EOCN-103.
S, EOCN-104S (Nippon Kayaku Co., Ltd.), UVR
-6650 (manufactured by Union Carbide), ESCN-1
95 (manufactured by Sumitomo Chemical Co., Ltd.).

Examples of the trishydroxyphenylmethane type epoxy resin include TACTICX-742 (manufactured by Dow Chemical Company) and Epicoat E1032H60 (manufactured by Yuka Shell Epoxy Co., Ltd.). Examples of the dicyclopentadiene phenol type epoxy resin include Epicron EXA-7200 (manufactured by Dainippon Ink and Chemicals, Inc.) and TACTIX-556 (manufactured by Dow Chemical Company).

As the bisphenol type epoxy resin,
For example, Epicoat 828, Epicoat 1001 (manufactured by Yuka Shell Epoxy), UVR-6410 (manufactured by Union Carbide), D.C. E. FIG. Bisphenol A type epoxy resin such as R-331 (manufactured by Dow Chemical Company), YD-8125 (manufactured by Toto Kasei), bisphenol such as UVR-6490 (manufactured by Union Carbide), YDF-8170 (manufactured by Toto Kasei) F-type epoxy resins and the like can be mentioned.

Examples of the biphenol type epoxy resin include a bixylenol type epoxy resin of YX-4000 (manufactured by Yuka Shell Epoxy Co., Ltd.) and YL-6121 (manufactured by Yuka Shell Epoxy Co., Ltd.). Examples of bisphenol A novolak type epoxy resin include Epiclon N-880 (manufactured by Dainippon Ink and Chemicals, Inc.),
Epicoat E157S75 (Yukaka Epoxy Co., Ltd.)
Manufactured).

Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.) and EXA-
4750 (manufactured by Dainippon Ink and Chemicals, Inc.). As the alicyclic epoxy resin, for example, EHPE-
3150 (manufactured by Daicel Chemical Industries, Ltd.). As the heterocyclic epoxy resin, for example, TEPI
C, TEPIC-L, TEPIC-H, TEPIC-S
(All manufactured by Nissan Chemical Industries, Ltd.).

The curing component (E) is used alone or as a mixture of two or more. The amount of the curing component (E) contained in the composition of the present invention is preferably 1 to 50% by weight, particularly preferably 3 to 50% by weight, when the solid content of the composition is 100% by weight.
~ 45% by weight.

Further, these curing components (E) include:
In order to further improve properties such as adhesion, chemical resistance, and heat resistance, it is particularly preferable to use an epoxy resin curing (acceleration) agent in combination. The amount of epoxy resin curing (acceleration) agent used is
0.01 to 100% by weight of the epoxy compound
It is preferably 25% by weight, particularly preferably 0.1 to 15% by weight. Commercially available products include, for example, C11Z, 2PH
Z, 2MZ-AZINE, 2E4MZ-AZINE, 2
Imidazole and its derivatives such as E4MZ-CN and 2MA-OK (all manufactured by Shikoku Chemical Industry Co., Ltd.), and tertiary amines such as hexa (N-methyl) melamine and 2,4,6-tris (dimethylamino) phenol Compounds, triazine compounds such as benzoguanamine, acetoguanamine and melamine, and acid anhydrides such as 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride And polyamines such as dicyandiamide, and organic phosphines such as triphenylphosphine. Of these, melamine and dicyandiamide are preferred.

The photosensitive resin composition of the present invention may further comprise, if necessary, for the purpose of improving properties such as adhesion and hardness.
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 amount used is preferably 60% by weight or less in the composition of the present invention, and particularly preferably 5 to 40% by weight.

Further, if necessary, coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black, and inhibition of polymerization of hydroquinone, hydroquinone monomethyl ether, etc. Agents, thickeners such as asbestos, benton, montmorillonite, etc., adhesion-imparting agents such as silicone-based, fluoropolymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based, silane coupling agents, etc. Additives such as agents can be used.

The photosensitive resin composition of the present invention comprises (B)
The components (C), (D), and (E), and if necessary, the inorganic filler and other components described above are preferably blended in the above proportions, and uniformly mixed, dissolved, dispersed, and the like by a roll mill or the like. It can be obtained by: In addition, a solvent may be used together if desired, mainly for adjusting the viscosity. This solvent may be a solvent used in the production of the components. Examples of the solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, glycol ethers such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether, ethyl acetate, and acetic acid. Esters such as butyl, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. γ-butyrolactone, N-methyl-2-pyrrolidone, etc. Organic solvents.

When the above-mentioned curing component (E) and a curing accelerator are mixed in advance with a solder resist composition to form a one-pack type, the viscosity tends to increase before application to a circuit board blank. The two-component type is composed of a main solution containing the flame-retardant energy ray-sensitive resin (B) as a main component and a curing accelerator and the like, and a curing agent solution mainly containing the curing component (E) ( The components (C) and (D) are added to one or both of them), and it is preferable to use them in a mixture at the time of use.

The photosensitive resin composition of the present invention is useful in liquid form as a resist ink, particularly a resist ink for printed circuit boards, and can also be used as a paint, coating agent, adhesive or the like.

The cured product of the present invention is obtained by photo-curing the above-mentioned photosensitive resin composition of the present invention by irradiation with energy rays such as ultraviolet rays, and by further heat-curing the photo-cured cured film. . Curing by irradiation with energy rays such as ultraviolet rays can be performed by a conventional method. When irradiating ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, an ultraviolet light emitting laser (for example, an excimer laser)
Or the like may be used. The cured product of the resin composition of the present invention is used for an electric / electronic component such as a printed board having a through hole as a permanent resist, for example.

The printed board of the present invention has a cured product layer of the above resin composition. The thickness of this cured product layer is 5 to 16
It is about 0 μm, preferably about 10 to 60 μm. The printed circuit board can be obtained, for example, as follows. That is, when a liquid resin composition is used, the printed wiring board is screen-printed, sprayed, roll-coated, electrostatically coated, curtain-coated, etc.
The composition of the present invention was applied to a thickness of 160 μm,
After drying at 0 to 110 ° C., the negative film is brought into direct contact with the coating film (or placed on the coating film in a non-contact state), irradiated with ultraviolet light, and the unexposed portion is diluted with a diluted alkaline aqueous solution described below. For example, development is performed by spraying, rocking immersion, brushing, scrubbing, or the like. Thereafter, the substrate is irradiated with ultraviolet rays as required, and then subjected to a heat treatment at 100 to 200 ° C., thereby obtaining a printed circuit board having a permanent protective film satisfying various characteristics.

Examples of the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Aqueous solutions of inorganic salts such as sodium bicarbonate, potassium bicarbonate, sodium metasilicate and potassium metasilicate, organic amine aqueous solutions such as trimethylamine, triethylamine, monomethanolamine, diethanolamine and triethanolamine, tetramethylammonium hydroxide, Ammonium hydroxides such as tetraethylammonium hydroxide and the like can be mentioned. These can be used alone or in combination of two or more. The temperature is 15
It can be arbitrarily adjusted between -45 ° C. A small amount of a surfactant, an antifoaming agent or the like may be mixed in this developer.

[0042]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but it should not be construed that the invention is limited thereto. Example 1 (Synthesis of flame-retardant energy ray-sensitive resin (B)) In a 1-liter flask, 94.5 g of carbitol acetate was used as a reaction solvent, and 250 parts by weight of a bisphenol-F type epoxy resin was used as an epoxy resin (a). Content of novolak type epoxy resin and 600 parts by weight of a novolak type epoxy resin and 150 parts by weight of 9,8-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as a compound of the formula (1) 314.7% by weight of an epoxy resin (epoxy equivalent: 361.7 g / equivalent)
g, as the unsaturated group-containing monocarboxylic acid (b), 63.3 g of acrylic acid, 0.24 g of 2-methylhydroquinone as a thermal polymerization inhibitor, 1.42 g of triphenylphosphine as a reaction catalyst, and 98 ° C. The reaction was carried out at a temperature for 24 hours to obtain an epoxy carboxylate resin solution.
Next, to this resin solution were added 122.0 g of tetrahydrophthalic anhydride as polybasic anhydride (d), 0.30 g of 2-methylhydroquinone as a thermal polymerization inhibitor, and 238.8 g of carbitol acetate as a reaction solvent,
A resin solution containing the flame-retardant energy ray-sensitive resin (B) of the present invention, which is reacted at a temperature of 95 ° C. for 6 hours (referred to as B-1)
I got The concentration of this resin solution was 60%, and the acid value of the resin solution was 54 mg · KOH / g.

Examples 2, 3, 4 According to the composition shown in Table 1, the numerical values are% by weight.
And kneading with a three-roll mill,
A resin composition was prepared. This is done by screen printing.
15 to 25 μm using a 100 mesh screen.
copper-clad glass patterned to a thickness of m
Apply to the entire surface of the epoxy board (thickness: about 0.5mm)
The membrane is dried in a hot air drier at 80 ° C. for 30 minutes. Then
Adhesion of negative film with resist pattern to coating film
UV exposure equipment (Oak Manufacturing Co., Ltd., Model HMW-
680 GW) (with an exposure dose of 20).
0mJ / cm^Two ). Then with a 1% aqueous sodium carbonate solution
2.0 kg / cm for 60 seconds ^Two Develop with the spray pressure of
Unexposed portions were dissolved and removed. About what was obtained, later
As described above, evaluation of developability, resolution, light sensitivity, and surface gloss
went. Then, heat harden for 60 minutes in a hot air dryer at 150 ° C.
The test piece having a cured film obtained by
Substrate warpage, adhesion, pencil hardness, solvent resistance,
Tested for acid resistance, heat resistance, gold plating resistance, and flammability
Was. Table 1 shows the results. The test method and evaluation
The valuation method is as follows.

(Developability) The following evaluation criteria were used.・: At the time of development, the ink was completely removed and development was possible. ×: Some parts are not developed during development.

(Resolution) A 50 μm negative pattern is adhered to the dried coating film, and the coated film is irradiated with ultraviolet rays having an integrated light amount of 200 mJ / cm ² . Next, it is developed with a 1% aqueous sodium carbonate solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the transfer pattern is observed with a microscope. The following criteria were used:・: The pattern edge is a straight line and is resolved. X: Peeling or pattern edges are jagged.

(Photosensitivity) A step tablet (manufactured by Kodak Co., Ltd.) was brought into close contact with the dried coating film, and the integrated light amount was 50
Irradiation exposure with ultraviolet rays of 0 mJ / cm ² is performed. Next, the film is developed with a 1% aqueous solution of sodium carbonate for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the number of steps of the coating film left undeveloped is confirmed. The following criteria were used: ○ ・ ・ ・ ・ ・ ・ 8 steps or more × ・ ・ ・ ・ 7 steps or less

(Surface gloss) 200 mJ
/ Cm ² UV irradiation. Next, it is developed with a 1% aqueous solution of sodium carbonate for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the cured film after drying is observed. The following criteria were used: ○ ・ ・ ・ No fogging is observed × ・ ・ ・ ・ Slight fogging is observed

(Substrate Warpage) The following criteria were used. ○ ・ ・ ・ No warpage is seen on the substrate × ・ ・ ・ ・ ・ ・ Warpage is seen on the substrate

(Adhesion) According to JIS K5400,
One hundred squares of 1 mm were formed on the test piece, and a peeling test was performed using cellophane tape. The state of peeling was evaluated by the following criteria. 〇 ・ ・ ・ ・ ・ ・ No peeling × ・ ・ ・ ・ ・ ・ Peel off

(Pencil hardness) Evaluation was made according to JIS K5400.

(Solvent Resistance) A test piece is immersed in isopropyl alcohol at room temperature for 30 minutes. After confirming that there was no abnormality in the appearance, a peeling test was carried out using cellophane tape and evaluated according to the following criteria. ○ ・ ・ ・ ・ ・ ・ No fogging observed ×× ・ ・ ・ Slight fogging observed

(Acid Resistance) A test piece is immersed in a 10% hydrochloric acid aqueous solution at room temperature for 30 minutes. After confirming that there is no abnormality in the appearance,
A peeling test was performed using cellotape and evaluated according to the following criteria. ○ ・ ・ ・ ・ ・ ・ No abnormality in the appearance of the coating film and no blistering or peeling × ・ ・ ・ ・ Body with blistering or peeling

(Heat resistance) A rosin-based plaque was applied to a test piece and immersed in a solder bath at 260 ° C. for 5 seconds. This was defined as one cycle, and three cycles were repeated. After allowing to cool to room temperature, a peeling test was performed using cellophane tape, and evaluated according to the following criteria. 〇: No abnormalities in the appearance of the coating film and no blistering or peeling ×: ・ ・ ・ Films with blistering or peeling

(Gold Plating Resistance) A test substrate was treated with an acidic degreasing solution (Mexex L-5, manufactured by McDermit Japan) at 30 ° C.
B in a 20 vol% aqueous solution), washed with water, then immersed in a 14.4 wt% aqueous ammonium persulfate solution at room temperature for 3 minutes, washed with water, and further placed in a 10 vol% aqueous sulfuric acid solution at room temperature for 1 minute. After immersion for a minute, it was washed with water.
Next, this substrate was immersed in a 30 ° C. catalyst solution (manufactured by Meltex, a 10 vol% aqueous solution of a metal plate activator 350) for 7 minutes, washed with water, and washed at 85 ° C. with a nickel plating solution (manufactured by Meltex, Melplate Ni-). 865M 2
After immersing in a 0 vol% aqueous solution (pH 4.6) for 20 minutes and performing nickel plating, the substrate was immersed in a 10 vol% aqueous sulfuric acid solution at room temperature for 1 minute and washed with water. Next, the test substrate is
Immersion for 10 minutes in a gold plating solution (available from Meltex, 15 vol% of Aurolectroles UP and 3 vol% of gold potassium cyanide, pH 6), electroless gold plating, washing with water, and further heating with 60 ° C. warm water. Dipped for minutes, washed with water and dried. A cellophane adhesive tape was adhered to the obtained electroless gold-plated evaluation substrate, and the state when peeled off was observed. ：: No abnormality at all. X: Some peeling was observed.

(Flammability) The composition was applied on a Teflon sheet, and the cured film obtained by performing the same operation as above was peeled from the Teflon sheet to obtain a cured resin film. The cured film was lit using a lighter. ：: The fire went out immediately. X: Burning was continued.

Table 1 Example Note 2 3 4 Flame retardant type energy ray photosensitive resin (B) B-1 35.67 35.67 35.67 Crosslinking agent (C) DPHA * 1 6.82 6.82 6.82 Photopolymerization initiator (D) Irgacure 907 * 2 4.77 4.77 4.77 DETX-S * 3 0.48 0.48 0.48 Curing component (E) YX-4000 * 4 8.18 4.00 EPPN-201 * 5 8.18 4.18 Curing accelerator Melamine 1.02 1.02 1.02 Additive BYK-354 * 6 0.68 0.68 0.68 BYK- 057 * 7 0.68 0.68 0.68 Filler Barium sulfate 20.45 20.45 20.45 Silica 7.50 7.50 7.50 Talc 0.68 0.68 0.68 Phthalocyanine green 0.55 0.55 0.55 Solvent Carbitol acetate 12.52 12.52 12.52 ―――――――――――――――――― ―――――――――――――― Evaluation items Developability ○ ○ ○ Resolution ○ ○ ○ Light sensitivity ○ ○ ○ Surface gloss ○ ○ ○ Substrate warpage ○ ○ ○ Adhesion ○ ○ ○ Pencil hardness 8H 8H 8H Solvent resistance ○ ○ ○ Acid resistance ○ ○ ○ Heat resistance ○ ○ ○ Gold plating resistance ○ ○ ○ Flammability ○ ○ ○

Note * 1 Nippon Kayaku: dipentaerythritol hexaacrylate * 2 Ciba-Geigy: 2-methyl- (4- (methylthio) phenyl) -2-morpholino-1-propane * 3 Nippon Kayaku: 2, 4-Diethylthioxanthone * 4 Oiled shell epoxy: Biphenol type epoxy resin * 5 Nippon Kayaku: Phenol novolak type epoxy resin * 6 Big Chemie: Leveling agent * 7 Big Chemie: Antifoaming agent

As is clear from the results shown in Table 1, the photosensitive resin composition of the present invention has high sensitivity and high resolution, can be developed with a dilute alkaline aqueous solution, and its cured film has a solder heat resistance. It is clear that the photosensitive resin composition for printed circuit boards is excellent in chemical resistance, gold plating resistance, etc., does not crack on the surface of the cured product, and has flame retardancy.

[0059]

According to the present invention, the photosensitive resin composition of the present invention can be used for forming a solder resist pattern by selectively exposing with a ultraviolet ray through a film on which a pattern is formed, and developing an unexposed portion. Excellent sensitivity, the resulting cured product is adhesive, pencil hardness, solvent resistance, acid resistance,
The composition also satisfies heat resistance, gold plating resistance, flame retardancy, PCT resistance, etc., and is particularly suitable for a liquid solder resist ink composition for printed wiring boards.

Claims (10)

[Claims] 1. An epoxy compound (a) having two or more epoxy groups in a molecule, an unsaturated group-containing monocarboxylic acid (b), and a compound represented by the following formula (1): (Wherein R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or an aryl group.) The epoxycarboxylate resin (A) obtained by reacting with a phosphorus compound (c) represented by the following formula: A flame-retardant energy ray-sensitive resin (B) to which an anhydride (d) has been added. 2. The flame-retardant energy ray-sensitive resin (B) according to claim 1, wherein the content of phosphorus is 0.8 to 8% by weight. 3. The method according to claim 1, wherein the phosphorus compound (c) is 9,8-dihydro-
The flame-retardant energy ray-sensitive resin (B) according to claim 1 or 2, which is 9-oxa-10-phosphaphenanthrene-10-oxide. 4. The epoxy compound (a) selected from the group consisting of a novolak type epoxy resin, a bisphenol type epoxy resin, a trisphenol methane type epoxy resin and a biphenol type epoxy resin. The flame-retardant energy ray-sensitive epoxy carboxylate resin (B) according to claim 3. 5. An unsaturated group-containing monocarboxylic acid (b) comprising:
An unsaturated group-containing monocarboxylic acid (b) selected from a maleimide compound obtained by reacting (meth) acrylic acid, cinnamic acid, and maleic anhydride with an aminocarboxylic acid. 5. The flame-retardant energy ray-sensitive epoxy carboxylate resin (B) according to any one of 4). 6. The polybasic anhydride (d) comprises succinic anhydride,
Maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, dihydro-3-[(6-oxide-6H-dibenz [c, e [1,2] oxaphosphorin-6
-Yl) methyl] -2,5-furandione, a polybasic anhydride selected from the group consisting of: a flame-retardant energy ray-sensitive resin (B) according to any one of claims 1 to 5, ). 7. The flame-retardant energy ray-sensitive resin (B) according to claim 1, wherein the solid acid acid value of the resin (B) is in the range of 50 to 150 mg · KOH / g. Combustible energy ray photosensitive resin (B). 8. A flame-retardant energy ray-sensitive resin (B), a cross-linking agent (C), a photopolymerization initiator (D) and a curing component (E) according to any one of claims 1 to 7. A) a photosensitive resin composition comprising: 9. A cured product of the energy ray-sensitive resin composition according to claim 8. 10. A printed circuit board having the cured product layer according to claim 9.