JP2001048956A - Flame retardant type energy beam photosensitive epoxycarboxylate 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, PCT resistance, etc., excellent in developmental property and photosensitivity. SOLUTION: This flame resistant type energy beam photosensitive epoxycarboxylate resin (B) is 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 and a composition thereof, particularly a photosensitive resin composition suitable for a liquid solder resist useful for manufacturing a printed circuit board, and a cured product thereof.

[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 photocurable liquid solder resists have been developed, and 50% or more are currently introduced.

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.

[0004]

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

[0005]

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 The energy ray-sensitive epoxy carboxylate resin (A), which is a reaction product of the acid (b) and the phosphorus compound (c) represented by the following formula (1), exhibits flame retardancy. By using the epoxy carboxylate resin (A), an energy ray-sensitive resin composition for a printed circuit board which exhibits high sensitivity and high resolution and is easily developed can be obtained, and the cured film thereof has excellent flame retardancy. The present invention was found to be excellent in solder heat resistance, chemical resistance, gold plating resistance, electrolytic corrosion resistance and the like, and completed the present invention. That is, the present invention provides (1) an epoxy compound (a) having two or more epoxy groups in a molecule and an unsaturated group-containing monocarboxylic acid (b).
And the following equation (1)

[0006]

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 epoxy carboxylate resin (A) obtained by reacting with a phosphorus compound (c)
(2) The flame-retardant energy ray-sensitive epoxy carboxylate resin (A) according to (1), wherein the phosphorus content is 0.8 to 8% by weight, and (3) the phosphorus compound (c) is 9,9. 8-
The flame-retardant energy ray-sensitive epoxy carboxylate resin (A) according to (1) or (2), which is dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and (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). Flame-retardant energy ray-sensitive epoxy carboxylate resin (A),

(5) Monocarboxylic acid containing unsaturated group (b)
Are unsaturated group-containing monocarboxylic acids (b) selected from maleimide compounds obtained by reacting (meth) acrylic acid, cinnamic acid, and maleic anhydride with an aminocarboxylic acid (1) to (1) to (4) The flame-retardant energy ray-sensitive epoxy carboxylate resin (A) according to any one of (4), (6) an epoxy compound (a) having two or more epoxy groups in a molecule and the above-mentioned formula (1) ) Is reacted to obtain a phosphorus-containing epoxy resin (d), and then the unsaturated group-containing monocarboxylic acid (b)
A method for producing a flame-retardant energy ray-sensitive epoxy carboxylate resin (A), characterized by reacting
(7) The flame-retardant energy ray-sensitive epoxy carboxylate resin (A), the crosslinking agent (B), the photopolymerization initiator (C), and the curing component (C) according to any one of (1) to (6). D) a photosensitive resin composition comprising: (8) a cured product of the photosensitive resin composition according to (7);
(9) A printed circuit board having the cured product layer according to (8).

BEST MODE FOR CARRYING OUT THE INVENTION

The flame-retardant energy ray-sensitive epoxy carboxylate resin (A) 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). It is a reaction product with the phosphorus compound (c) represented by the formula (1). The content of phosphorus in the epoxy carboxylate resin is preferably in the range of 0.8 to 8% by weight. If this amount is less than 0.8% by weight, the flame retardancy becomes insufficient, and if it exceeds 8% by weight,
Since the amount of the unsaturated group-containing monocarboxylic acid (b) to be described later is relatively low, the photosensitivity is inferior, and the crosslink 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 preferred.

Examples of the novolak type epoxy resin include phenol novolak type epoxy resin and cresol novolak type epoxy resin. 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
(Manufactured by Yuka Shell Epoxy Co., Ltd.) and RE-306 (manufactured by Nippon Kayaku Co., Ltd.). As the cresol novolak type epoxy resin, for example, Epicron N-695
(Manufactured by Dainippon Ink and Chemicals, Inc.), EOCN-102
S, EOCN-103S, EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), UVR-6650 (manufactured by Union Carbide), ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

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, R ₁ and R ₂ each represent a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group,
-Butyl group, sec-butyl group, an alkyl group such as a tert-butyl group, or a compound that is an aryl group such as a phenyl group, a tolyl group, and a naphthyl group,
Among them, 9,8-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is particularly preferred.

The method for producing the flame-retardant energy ray-sensitive epoxy carboxylate resin (A) of the present invention includes, for example, an epoxy compound (a) having two or more epoxy groups in a molecule, an unsaturated group-containing monomer A method for simultaneously reacting a carboxylic acid (b) and a phosphorus compound (c) of the formula (1), an epoxy compound (a) having two or more epoxy groups in a molecule and an unsaturated group-containing monocarboxylic acid (b). Is reacted first and then the phosphorus compound (c) of the formula (1) is reacted, or the epoxy compound (a) having two or more epoxy groups in the molecule and the phosphorus compound (c) of the formula (1) Is reacted first, and then the 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 (d) is obtained by reacting a calculated amount such that the phosphorus content in the fuel-type energy-sensitive photosensitive epoxy carboxylate resin (A) 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, it is 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 octanoate, octane Zirconium acid and the like. The method for obtaining the phosphorus-containing epoxy resin (d) can be performed by the method described in JP-A-11-166035.

Next, the unsaturated group-containing monocarboxylic acid (b) is preferably added in an amount of 0.5 to 1.5 equivalents to 1 equivalent of the epoxy group of the obtained phosphorus-containing epoxy resin (d).
Particularly preferably, 0.7 to 1.1 equivalents are reacted. Further, it is preferable to use a catalyst in order to promote the reaction.
-10% by weight. The reaction temperature at that time is 60 to 150
C., and the reaction time is preferably 5 to 60 hours. Examples of the catalyst used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate,
And zirconium octoate.

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

Examples of the crosslinking agent (B) used in the photosensitive resin composition of the present invention include (meth) acrylate compounds, azide compounds, diazo compounds and nitro compounds. A (meth) acrylate compound which can be radically polymerized by (C) and can easily undergo a crosslinking reaction with the flame-retardant energy ray-sensitive epoxy carboxylate resin (A) is particularly preferred. (Meta)
As the acrylate compound, for example, 2-hydroxyethyl (meth) acrylate, phenoxyethyl (meth)
Acrylate, acryloyl monophorin, isobornyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, penta Erythritol 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 (B) used in the photosensitive resin composition of the present invention is preferably 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 (C) 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 (C) may 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 (C) 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 (C).

The curing component (D) used in the present invention comprises:
It reacts thermally with the flame-retardant energy ray-sensitive epoxy carboxylate resin (A) during heat curing after development to impart alkali resistance, solvent resistance, heat resistance and electrical insulation to the cured coating film. . For these curing components (D), 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, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol type epoxy resin, biphenol type epoxy resin, and bisphenol type epoxy resin. A-type novolak type epoxy resin, naphthalene skeleton-containing epoxy resin, heterocyclic epoxy resin, and these epoxy resins and 9,8-
An epoxy resin obtained by reacting dihydro-9-oxa-10-phosphaphenanthrene-10-oxide can be used.

Examples of the phenol novolak type epoxy resin include, for example, Epicron 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) and YL-6121 (manufactured by Yuka Shell Epoxy). 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) 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 (D) is used alone or as a mixture of two or more. The amount of the curing component (D) contained in the composition of the present invention is preferably from 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 (D) 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 polymerization inhibition of hydroquinone, hydroquinone monomethyl ether, etc. Agents, thickeners such as asbestos, benton, montmorillonite, etc., defoaming agents such as silicones and fluoropolymers and / or adhesion imparting agents such as leveling agents, imidazoles, thiazoles, triazoles and silane coupling agents Additives such as agents can be used.

The photosensitive resin composition of the present invention comprises (A)
The components (B), (C), and (D), and if necessary, the inorganic filler and the other components described above are preferably mixed in the above-described ratio, and uniformly mixed, dissolved, and dispersed 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.

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 further obtained by 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 developed using a developing solution described below, for example. Develop by spraying, rocking immersion, brushing, scrubbing, etc. 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 developer include ketones such as ethyl methyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and the like. Glycol ethers, ethyl acetate, butyl acetate, isoamyl acetate, butyl cellosolve acetate,
Esters such as carbitol acetate and propylene glycol monomethyl ether acetate; and organic solvents such as γ-butyrolactone and N-methyl-2-pyrrolidone. These can be used alone or in combination of two or more. In addition, the temperature is 15 to
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.

[0040]

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 epoxy carboxylate resin (A)) Bisphenol-F was used as an epoxy compound (a) having two or more epoxy groups in a molecule in a 2 liter flask.
The epoxy resin of 250 parts by weight and the novolak type epoxy resin of 600 parts by weight were charged, and stirred and dissolved at a temperature of 60 ° C. while blowing nitrogen gas. Then, as a compound of the formula (1), 150 parts by weight of 9,8-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 2% by weight of triphenylphosphine as a reaction catalyst.
In addition, the mixture was reacted at a temperature of 150 ° C. for 5 hours to obtain a phosphorus-containing epoxy resin (d). The phosphorus content of the obtained resin was 2% by weight, and the epoxy equivalent was 361.7 g / equivalent. Next, 399.6 g of the phosphorus-containing epoxy resin (d) obtained in a 1-liter flask, 120.0 g of carbitol acetate as a reaction solvent, and 80.4 g of acrylic acid as an unsaturated group-containing monocarboxylic acid (b), 0.30 of 2-methylhydroquinone as a thermal polymerization inhibitor
g, 1.80 of triphenylphosphine as a reaction catalyst
g, and reacted at a temperature of 98 ° C. for 24 hours to obtain a resin solution (referred to as A-1) containing the flame-retardant energy ray-sensitive epoxy carboxylate resin (A) of the present invention. The concentration of this resin solution was 60%.

Examples 2, 3, and 4 Each component was blended according to the blending composition shown in Table 1 (numerical values are% by weight) and kneaded with a three-roll mill to prepare a photosensitive resin composition of the present invention. This was screen-printed using a 100-mesh screen at 15 to 25 μm.
m is applied to the entire surface of a copper-clad glass epoxy substrate (thickness: about 0.5 mm) which is patterned to have a thickness of m, and the coating film is dried with a hot air drier at 80 ° C. for 30 minutes. Then
A negative film having a resist pattern is brought into close contact with the coating film, and an ultraviolet exposure apparatus (Oak Manufacturing Co., Ltd., model HMW-
680 GW) (with an exposure dose of 20).
0 mJ / cm ² ). Next, development was performed with methyl isobutyl ketone and isopropyl alcohol (weight ratio: 50/50) for 30 seconds at a spray pressure of 1.0 kg / cm ² to dissolve and remove unexposed portions. The obtained product was evaluated for developability, resolution, photosensitivity, and surface gloss as described below. Thereafter, heat curing was performed for 60 minutes in a hot air dryer at 150 ° C., and the test piece having the obtained cured film was subjected to substrate warpage, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, and heat resistance as described below. Gold plating and flammability tests were performed.
Table 2 shows the results.

Table 1 Example Note 2 3 4 Flame retardant type energy ray photosensitive resin (A) A-1 35.67 35.67 35.67 Comparative resin Crosslinking agent (B) DPHA * 1 6.82 6.82 6.82 Photopolymerization initiator (C) Irgacure 907 * 2 4.77 4.77 4.77 DETX-S * 3 0.48 0.48 0.48 Curing component (D) 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 -------------------------- −−−−−−−−−−−−−−−−−− Developability ○ ○ ○ Resolution ○ ○ ○ Photosensitivity ○ ○ ○ 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

The test method and the evaluation method are 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, development is performed with methyl isobutyl ketone and isopropyl alcohol (weight ratio: 50/50) for 30 seconds at a spray pressure of 1.0 kg / cm ² , and a 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.

(Light Sensitivity) 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, methyl isobutyl ketone and isopropyl alcohol (weight ratio: 5
(0/50) for 30 seconds at a spray pressure of 1.0 kg / cm ² , and the number of coating layers remaining without development is confirmed. The following criteria were used: ○ ・ ・ ・ ・ ・ ・ 8 steps or more × ・ ・ ・ ・ 7 steps or less

(Surface Gloss) After drying, the coating
/ Cm ² UV irradiation. Next, methyl isobutyl ketone and isopropyl alcohol (weight ratio: 50/5)
0) for 30 seconds with a spray pressure of 1.0 kg / cm ² and observe the dried cured film. The following criteria were used: ○ ・ ・ ・ ・ ・ ・ No fogging observed ×× ・ ・ ・ Slight fogging observed

(Substrate Warpage) The following criteria were used. ○ ・ ・ ・ ・ ・ ・ Surface is not seen on the substrate ×× ・ ・ ・ Surve is seen on the substrate

(Adhesion) According to JIS K5400,
100 test pieces were made with 1 mm-thick squares, and a peeling test was performed using Cellotape (registered trademark). The state of peeling was evaluated by the following criteria.・: No peeling × :: Peeling (pencil hardness) Evaluation was performed 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 (registered trademark) sheet, and a 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.

As is clear from the results in Table 2, 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 has excellent chemical resistance, gold plating resistance, etc., does not crack on the surface of the cured product, has flame retardancy, and does not warp even when a thinned substrate is used. It is clear that this is a conductive resin composition. Also, the PCT resistance is good.

[0057]

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.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J011 QA03 QA13 QA22 QA23 QA24 QA34 QA39 QA42 QB16 QB19 QB20 QB22 SA01 SA20 SA21 SA31 SA42 SA51 SA63 SA64 SA78 SA79 SA80 SA83 UA01 VA01 WA01 WA02 WA06 4J027 AE03 AE03 AE04 AJ08 BA07 BA08 BA13 BA19 BA23 BA24 BA26 BA27 CB10 CC03 CC05 CD08 CD09 CD10 4J036 AC02 AD07 AD08 AF06 CA21 CB22 CC02 EA04 EA09 FA10 FA12 HA01 JA01 JA06 JA09 5E314 AA27 AA31 AA32 CC01 FF01 GG08 GG11 GG14GG

Claims (9)

[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.) A flame-retardant energy ray-sensitive epoxy carboxylate resin obtained by reacting with a phosphorus compound (c) represented by the following formula: (A). 2. The flame-retardant energy ray-sensitive epoxy carboxylate resin (A) according to claim 1, wherein the phosphorus content 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 epoxy carboxylate resin (A) according to any one of claims 1 and 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 (A) 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 (A) according to any one of 4. 6. A phosphorus-containing epoxy resin (d) by reacting an epoxy compound (a) having two or more epoxy groups in the molecule with the phosphorus compound (c) according to claim 1.
Then, a method for producing a flame-retardant energy ray-sensitive epoxy carboxylate resin (A), which comprises reacting with an unsaturated group-containing monocarboxylic acid (b). 7. The flame-retardant energy ray-sensitive epoxy carboxylate resin (A) according to any one of claims 1 to 6, a crosslinking agent (B), a photopolymerization initiator (C) and curing. A photosensitive resin composition comprising component (D). 8. A cured product of the photosensitive resin composition according to claim 7. 9. A printed circuit board having the cured product layer according to claim 8.