JP2001164095A - Photosensitive resin composition and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin composition excellent in dispersibility, drying properties and environmental safety and providing a fine pattern excellent in developability, photosensitivity, adhesion, pencil hardness, solvent, acid, heat and gold plating resistances. SOLUTION: This photosensitive resin composition comprises a mixed solvent (E) composed of a dialkyl glutarate, a dialkyl succinate and a dialkyl adipate in the photosensitive resin composition in the photosensitive resin composition used when producing electronic circuit boards.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition and a cured product thereof, and more particularly to a photosensitive resin composition which can be developed with an aqueous alkali solution and is useful for manufacturing a printed circuit board.

[0002]

2. Description of the Related Art Conventionally, in producing a photosensitive resin composition, a resin is synthesized in a highly soluble organic solvent as a reaction solvent for producing a resin constituting the photosensitive resin composition. In preparing a photosensitive resin composition, in order to knead a filler or the like with a resin, raw materials are kneaded with a mill such as a dissolver or a three-roll mill to obtain a resin composition.

On the other hand, in manufacturing a printed wiring board, a liquid photosensitive material containing a volatile component (hereinafter referred to as a solvent) is used in order to uniformly apply a non-volatile component (hereinafter referred to as a solid component) in the photosensitive resin composition to the substrate. Spin coating method, screen printing method, spray method, roll coating method,
Adopt coating methods such as electrostatic coating method and curtain coating method,
Next, in a step called prebaking, most of the solvent is volatilized at an appropriate temperature to obtain a uniform film composed of solids. For example, in the spin coating method, although depending on the viscosity, about 60 to 90% by weight of a solvent is generally contained in the photosensitive resin composition. It is said that in a screen printing method that can be performed, about 10 to 40% by weight of a solvent must be contained in the photosensitive resin composition.

[0004] Solvents contained in the photosensitive resin composition include good solubility in resin (ability to dissolve resin), good dispersibility of filler and the like (ability to disperse filler and the like), moderate From the viewpoint of having a volatilization rate, etc.
Solvents having an ethylene glycol skeleton are mainly used.
However, it is thought that this (di) ethylene glycol skeleton solvent generates methoxyacetic acid derivatives when decomposed in vivo, and it is necessary to take great care to handle these solvents and to reduce It is said that sufficient countermeasures against pollution are necessary.

[0005]

SUMMARY OF THE INVENTION Photosensitization using a solvent which has good solubility in resins, good dispersibility of fillers and the like, an appropriate rate of volatilization, is completely decomposed in vivo, and is environmentally friendly. The development of a conductive resin composition is desired.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a photosensitive resin composition used in manufacturing a printed wiring board uses a solvent composed of a specific chemical. As a result, the inventors have found that the above object can be solved, and have completed the present invention.

That is, the present invention provides (1) a photosensitive resin composition for producing an electronic circuit board, which comprises a mixed solvent (E) comprising a dialkyl glutarate, a dialkyl succinate and a dialkyl adipate; ) An ethylenically unsaturated group-containing polycarboxylic acid resin (A), a photocrosslinking agent (B),
The mixed solvent (E) of the photosensitive resin composition (3) according to (1), which contains the photopolymerization initiator (C) and the epoxy resin (D).
Is a ratio of dialkyl glutarate 50
~ 70 wt%, dialkyl succinate 10 ~ 30 wt%,
The photosensitive resin composition (4) according to (1) or (2), which is 5 to 30% by weight of the dialkyl adipate, is dimethyl glutarate (1) to (3).
The photosensitive resin composition according to any one of (1) to (3), wherein the dialkyl succinate is dimethyl succinate.
The photosensitive resin composition (7) according to any one of (1) to (3), wherein the dialkyl adipate is dimethyl adipate, wherein the ethylenically unsaturated group-containing polycarboxylic acid resin (A) is an epoxy ( (1) The photosensitive resin composition (8) according to any one of (1) to (7), which is a polybasic acid anhydride adduct (a) of an acrylate resin. (9) A printed board having a layer of the cured product according to (8).

[0008]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail. The photosensitive resin composition of the present invention is characterized by containing a mixed solvent (E) composed of dialkyl glutarate, dialkyl succinate and dialkyl adipate as an essential component, and particularly containing an ethylenically unsaturated group. A photosensitive resin composition containing a polycarboxylic acid resin (A), a photocrosslinking agent (B), a photopolymerization initiator (C), an epoxy resin component (D), and the mixed solvent (E). The term “photosensitivity” as used herein refers to a property of being polymerized and cured in the presence or absence of a polymerization initiator by irradiation with an energy beam such as an electron beam or an ultraviolet ray.

The ratio of each component constituting the mixed solvent (E) contained in the photosensitive resin composition of the present invention is 50 to 70% by weight of dialkyl glutarate, 10 to 30% by weight of dialkyl succinate, and adipic acid. Dialkyl 5 to 30% by weight is particularly preferred. If the amount deviates from this amount, there is no particular problem in terms of the solubility of the resin and the dispersibility of the filler, but when the photosensitive resin composition of the present invention is applied to the substrate, the following problems occur due to the volatilization rate. There is a possibility that. When the solvent volatilization rate is low: The time for volatilizing the solvent is long, and there is a concern that the solid content is thermally cured. When the solvent volatilization rate is high: the thickness of the solid content may not be uniform.

Specific examples of the dialkyl glutarate, which is a component of the mixed solvent (E) contained in the photosensitive resin composition of the present invention, include dimethyl glutarate, diethyl glutarate, dipropyl glutarate, dibutyl glutarate. And the like, but dimethyl glutarate is particularly preferred in view of the volatilization rate, the solubility of the resin, and the dispersibility of the filler. Alkyl groups of ₅ or more have a slightly poor volatility, a long processing time after coating, a solvent remaining in solid components, and a film mask sticking to a coated surface during exposure,
There is a possibility that the adhesion may be reduced and a problem such as the inability to transfer the fine line pattern may occur.

Specific examples of the dialkyl succinate which is a component of the mixed solvent (E) contained in the photosensitive resin composition of the present invention include dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl succinate. And the like, but dimethyl succinate is particularly preferred in view of the volatilization rate, the solubility of the resin, and the dispersibility of the filler. C ₅ or more alkyl groups, the volatility is slightly poor, the processing time after coating is long, or the solvent remains in the solid component, at the time of exposure,
There is a possibility that the film mask may stick to the application surface, or the adhesion may be reduced, and a problem such as a thin line pattern being unable to be transferred.

Specific examples of the dialkyl adipate which is a component of the mixed solvent (E) contained in the photosensitive resin composition of the present invention include dimethyl adipate, diethyl adipate, dipropyl adipate and dibutyl adipate. And the like, and dimethyl adipate is particularly preferred in view of the volatilization rate, the solubility of the resin, and the dispersibility of the filler. C ₅ or more alkyl groups, the volatility is slightly poor, the treatment time after coating is long, or the solvent remains in the solid content,
At the time of exposure, there is a risk that a film mask may stick to the coating surface, or the adhesion may be low, causing a problem that a fine line pattern cannot be transferred.

The mixed solvent (E) contained in the photosensitive resin composition of the present invention further contains a (di) propylene glycol skeleton which is safe for the global environment in order to further adjust the solubility and the volatilization rate. And a solvent such as propionate can be added as appropriate. Can be used (di)
Examples of the solvent having a propylene glycol skeleton include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, and the like. Examples of usable propionate esters include, for example, methyl propionate, ethyl propionate, propyl propionate, methyl methoxypropionate, and ethyl methoxypropionate. In the present invention, the mixed solvent (E) is used as the mixed solvent (E) when producing the ethylenically unsaturated group-containing polycarboxylic acid resin (A). It can also be contained in the photosensitive resin composition.

The dialkyl glutarate constituting the mixed solvent (E) contained in the photosensitive resin composition of the present invention,
Both dialkyl succinates and dialkyl adipates are particularly excellent in biodegradability, and are known as Decines Resea.
Research of rc Center (614/5942 / JN
/ FD) has confirmed complete biodegradability. As a result of a local skin irritation test and an eye irritation test using rabbits, no irritation was observed. In addition, in an acute oral toxicity test and an acute dermal toxicity test using mice Results of> 2 g / kg have been reported.

In the present invention, a polybasic acid anhydride adduct (a) of an epoxy (meth) acrylate resin, which is a preferred example of the ethylenically unsaturated group-containing polycarboxylic acid resin (A), has two or more per molecule. (Meth) acrylic acid obtained by reacting a compound having an epoxy group with (meth) acrylic acid. As a method for synthesizing the ethylenically unsaturated group-containing polycarboxylic acid resin (A), for example, in the above-mentioned mixed solvent (E), one equivalent of the epoxy group of the epoxy compound having two or more epoxy groups in the molecule is used. And (meth) acrylic acid is preferably 0.6 to
The reaction is carried out using 1.3 equivalents, particularly preferably 0.8 to 1.1 equivalents. 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 total weight of the reaction raw materials. In order to prevent thermal polymerization during the reaction, it is preferable to use a thermal polymerization inhibitor, the amount of which is used, based on the total weight of the reaction raw materials.
Preferably it is 0.01 to 1% by weight. The reaction temperature at that time is 60 to 150 ° C, and the reaction time is usually 5 to
60 hours. Catalysts that can be used in this reaction include:
Examples include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, zirconium octoate and the like.
Examples of the thermal polymerization inhibitor that can be used include, for example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, tert-butyl catechol,
Pyrogallol and the like.

In the reaction of ring-opening addition of a polybasic acid anhydride to the thus obtained reaction product, the polybasic acid anhydride is added in an amount of 0.1 equivalent per hydroxyl group to the alcoholic hydroxyl group in the reaction product. It is obtained by reacting 1 to 1.0 equivalent. If the amount is out of this range, gelation or the like may occur during the reaction, or plating resistance or solvent resistance may be impaired. The reaction temperature is preferably from 60 to 150 ° C, and the reaction time is from 1 to 10 hours. The acid value of the ethylenically unsaturated group-containing polycarboxylic acid resin (A) thus obtained (mg
KOH / g) is preferably from 30 to 150, and particularly preferably from 40 to 140. Specific examples of polybasic acid anhydrides that can be used include, for example, succinic anhydride, maleic anhydride,
Examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, trimellitic anhydride, and pyromellitic anhydride.

Specific examples of the compound having two or more epoxy groups in a molecule include a phenol novolak epoxy resin, a cresol novolak epoxy resin, a trisphenolmethane epoxy resin, a bisphenol epoxy resin and the like. .

Specific examples of phenol novolak type epoxy resins that can be used include, for example, RE-306, EPPN
-200 series (Nippon Kayaku Co., Ltd.), Epicron N
-770 (manufactured by Dainippon Ink and Chemicals, Inc.); E. FIG.
N438 (manufactured by Dow Chemical Company), Epicoat 154
(Made by Yuka Shell Epoxy Co., Ltd.) and the like. Specific examples of the cresol novolak type epoxy resin that can be used include, for example, EOCN-102S and EOCN-103.
S, EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), Epicron N-695 (manufactured by Dainippon Ink and Chemicals, Inc.), U
VR-6650 (manufactured by Union Carbide), ESCN
-195 (manufactured by Sumitomo Chemical Co., Ltd.).

Specific examples of the trishydroxyphenylmethane type epoxy resin that can be used include, for example, EPPN-5
00 series (Nippon Kayaku Co., Ltd.), TACTICX-
742 (manufactured by Dow Chemical Company), Epicoat E1032
H60 (manufactured by Yuka Shell Epoxy Co., Ltd.) and the like.

Specific examples of bisphenol type epoxy resins that can be used include, for example, Epicoat 828, Epicoat 1001 (made by Yuka Shell Epoxy), UVR-6410
(Manufactured by Union Carbide), D.I. E. FIG. R-331 (manufactured by Dow Chemical), YD-8125 (manufactured by Toto Kasei)
Bisphenol A type epoxy resin, UVR-649
Bisphenol F type epoxy resin such as No. 0 (manufactured by Union Carbide) and YDF-8170 (manufactured by Toto Kasei).

Specific examples of the photocrosslinking agent (B) that can be used in the photosensitive resin composition of the present invention include, 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, pentaerythritol tri (meth) acrylate, penta Examples include acrylates such as erythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol poly (meth) acrylate. The amount of these is generally 2 to 40 parts by weight, preferably 5 to 30 parts by weight, when the solid content in the resin composition is 100 parts by weight.

Specific examples of the photopolymerization initiator (C) that can be used in the present invention can be divided into a photoradical polymerization initiator (C-1) and a cationic photopolymerization initiator (C-2).
Here, the photo-radical polymerization initiator (C-1) includes visible light,
Irradiation with energy rays such as ultraviolet rays, X-rays, and electron beams generates active radical species and causes the ethylenically unsaturated groups present in the ethylenically unsaturated group-containing polycarboxylic acid resin (A) and the photocrosslinking agent (B). It acts to initiate a polymerization reaction of a saturated group.

Photoradical polymerization initiator (C-1) that can be used
As specific examples of, for example, acetophenone, 2,2-diethoxy-2-phenylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone,
-Methyl-1- [4- (methylthio) phenyl] -2-
Morpholino-propan-1-one, 2-benzyl-2-
Acetophenones such as dimethylamino-1- (4-morpholinophenyl) -butanone-1, benzophenone, p
Benzophenones such as -chlorobenzophenone, p, p-bisdimethylaminobenzophenone, p, p-bisdiethylaminobenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, benzyl, benzoin, benzoin methyl ether, benzoin isobutyl ether and the like; Benzoin ethers, ketals such as benzyldimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone,
Thioxanthones such as -isopropylthioxanthone,
Anthraquinone, 2,4,5-triarylimidazole dimer, 2,4,6-tris (trichloromethyl)-
s-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

Further, a cationic photopolymerization initiator (C-2)
Is an epoxy resin that generates a Bronsted acid or a Lewis acid by irradiating energy rays such as visible light, ultraviolet light, X-rays, and electron beams, and remains on the ethylenically unsaturated group-containing polycarboxylic acid resin (A). Acts to initiate the polymerization reaction of the group.

Photocationic polymerization initiator that can be used (C-2)
Examples thereof include diazonium salts, sulfonium salts, iodonium salts and the like. Specific examples thereof include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium hexafluoroborate,
Triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroborate, 4,4'-bis [bis (2-hydroxyethoxyphenyl) sulfonio] phenylsulfide bishexafluorophosphate, diphenyliodonium Hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate and the like can be mentioned. (For details on cationic photopolymerization, see the section on photocationic polymerization in “Photopolymer Technology: Ao Yamaoka and Mototaro Nagamatsu,” published by Nikkan Kogyo Shimbun.)

These photopolymerization initiators (C) can be used alone or in combination of two or more. The amount is preferably 0.1 to 30 parts by weight when the solid content in the resin composition is 100 parts by weight, more preferably,
1 to 20 parts by weight.

Further, these photopolymerization initiators (C) are:
N, N-dimethylaminobenzoic acid ethyl ester, N, N
N-dimethylaminobenzoic acid isoamyl ester, N,
Pentyl N-dimethylaminobenzoate, 4,
It can be used in combination with a sensitizer such as 4'-bis (N, N-dimethylamino) -benzophenone and 4,4'-bis (N, N-dimethylamino) -benzophenone. As the amount of the sensitizer, the photopolymerization initiator (C)
Is preferably 0 to 50% by weight based on the total weight of

The epoxy resin (D) used in a preferred embodiment of the present invention reacts with a carboxyl group in the acrylic copolymer resin during heat curing after exposure and development to give a cured coating film with alkali resistance and resistance to heat. It acts to impart solvent properties, heat resistance and electrical insulation. Examples of the epoxy resin (D) that can be used include a phenol novolak epoxy resin, a cresol novolak epoxy resin, a trisphenolmethane epoxy resin, a dicyclopentadiene phenol epoxy resin, a bisphenol-A epoxy resin, and a bisphenol-F epoxy resin. An epoxy resin, a biphenol type epoxy resin, a bisphenol-A novolak type epoxy resin, a naphthalene skeleton-containing epoxy resin, a heterocyclic epoxy resin, and the like can be given. As commercial products corresponding to these, the same products as described above can be used. The epoxy resin (D) is used singly or as a mixture of two or more kinds. The amount of the epoxy resin (D) contained in the photosensitive resin composition of the present invention is 10% of the solid content in the resin composition.
When it is 0 parts by weight, it is preferably 1 to 50 parts by weight, particularly preferably 3 to 45 parts by weight. These uses are also useful in further improving various properties as a solder resist such as adhesion, heat resistance, and plating resistance.

Examples of usable phenol novolak type epoxy resins include, for example, RE-306 and EPPN-200.
Series (Nippon Kayaku Co., Ltd.), Epicron N-770
(Manufactured by Dainippon Ink and Chemicals, Inc.); E. FIG. N438
(Manufactured by Dow Chemical Company) and Epicoat 154 (manufactured by Yuka Shell Epoxy Co., Ltd.). Examples of usable cresol novolak type epoxy resin include, for example, EOC
N-102S, EOCN-103S, EOCN-104
S (manufactured by Nippon Kayaku Co., Ltd.), Epicron N-695 (manufactured by Dainippon Ink and Chemicals, Inc.), UVR-6650 (manufactured by Union Carbide), ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.), etc. Is mentioned.

Examples of the trishydroxyphenylmethane type epoxy resin include EPPN-500 series (manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Company), and Epicoat E1032H60 (manufactured by Yuka Shell Epoxy Co., Ltd.). ) And the like.

Examples of bisphenol type epoxy resins that can be used include, for example, Epikote 828 and Epikote 1001
(Manufactured by Yuka Shell Epoxy), UVR-6410 (manufactured by Union Carbide), D.I. 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 usable phenol novolak type epoxy resins include, for example, Epicron N-770 (manufactured by Dainippon Ink and Chemicals, Inc.), D.N. 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 biphenol type epoxy resin which can be used include a bixylenol type epoxy resin of YX-4000 (manufactured by Yuka Shell Epoxy Co., Ltd.) and YL-6
121 (made by Yuka Shell Epoxy Co., Ltd.) and the like. Examples of the bisphenol A novolak type epoxy resin that can be used include, for example, Epicron N-880 (manufactured by Dainippon Ink and Chemicals, Inc.) and Epicoat E157S75 (manufactured by Yuka Shell Epoxy).

Examples of usable naphthalene skeleton-containing epoxy resins include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.)
XA-4750 (manufactured by Dainippon Ink and Chemicals, Inc.) and the like. As the alicyclic epoxy resin that can be used, for example, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.)
And the like. Examples of the usable heterocyclic epoxy resin include, for example, TEPIC, TEPIC-L, TEPIC-
H, TEPIC-S (all manufactured by Nissan Chemical Industries, Ltd.)
And the like.

Further, these epoxy resins (D) include:
In order to further improve properties such as adhesion, chemical resistance, and heat resistance, it is preferable to use an epoxy resin curing (acceleration) agent in combination. The amount of the epoxy resin curing (acceleration) agent used is 0.01 to 2 parts by weight per 100 parts by weight of the epoxy resin (D).
The amount is preferably 5 parts by weight, particularly preferably 0.1 to 15 parts by weight. Commercially available curing (acceleration) agents include, for example,
C11Z, 2PHZ, 2MZ-AZINE, 2E4MZ
-AZINE, 2E4MZ-CN, 2MA-OK (all manufactured by Shikoku Chemicals Co., Ltd.) and derivatives thereof, hexa (N-methyl) melamine, 2,4,6-
Tertiary amines such as tris (dimethylamino) phenol; triazine compounds such as benzoguanamine, acetoguanamine and melamine; 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1 Anhydrides such as 2,2-dicarboxylic anhydride, polyamines such as dicyandiamide, and organic phosphines such as triphenylphosphine. Among these, preferred are melamine and dicyandiamide.

The photosensitive resin composition of the present invention has a coating suitability,
For the purpose of further improving properties such as heat resistance, adhesion, and hardness, barium sulfate, barium titanate, silicon oxide powder,
Finely divided silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide,
A filler such as aluminum hydroxide, mica powder, and Teflon powder can be contained. The amount used is 60 when the solid content in the photosensitive resin composition of the present invention is 100 parts by weight.
It is preferably at most 5 parts by weight, particularly preferably from 5 to 50 parts by weight.

Further, if necessary, the photosensitive resin composition of the present invention may be colored with phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, or the like. Agent, hydroquinone, hydroquinone monomethyl ether, tert-
Polymerization inhibitors such as butylcatechol, pyrogallol, phenothiazine, etc., thickeners such as asbestos, olben, bentone, montmorillonite, silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole Additives such as an adhesion promoter such as a system, a triazole, and a silane coupling agent can be used.

The resin composition of the present invention comprises (A), (B),
(C), (D) and (E) components or (A) (E)
The solution, the components (B), (C), and (D) and, if necessary, the inorganic filler and the above-mentioned components are blended so as to have the above-mentioned ratio, and then uniformly mixed and dissolved by a roll mill or the like. ,
It is obtained by dispersion or the like. In the case where the epoxy resin (D) and the curing accelerator are mixed in advance with the photosensitive resin composition to form a one-pack type, the viscosity tends to increase before application to the circuit board blank. A two-component composition comprising a base solution mainly containing an unsaturated group-containing polycarboxylic acid resin (A) and a curing agent solution mainly containing an epoxy resin (D),
When used, it is preferable to mix them.

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, but can also be used as a paint, coating agent, adhesive or the like.

The cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention by irradiation with energy rays such as ultraviolet rays. Curing by irradiation with energy rays such as ultraviolet rays can be performed by a conventional method. In irradiating the ultraviolet rays, an ultraviolet generator such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, and an ultraviolet light emitting laser (for example, an excimer laser) may be used. The cured product of the photosensitive resin composition of the present invention is used for, for example, electric / electronic parts such as printed boards having through holes as permanent resists.

The printed board of the present invention has a cured layer of the photosensitive resin composition of the present invention. The thickness of the cured product layer is usually about 5 to 160 μm, more 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 present invention is applied to a substrate for printed wiring with a film thickness of 5 to 160 μm by a method such as a screen printing method, a spray method, a roll coating method, an electrostatic coating method, and a curtain coating method. Is applied, and the coating film is baked at 60 to 110 ° C. to evaporate the mixed solvent (E). Thereafter, 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 rays, and sprayed on the unexposed portion using a dilute alkaline aqueous solution (developer) described later, for example, by spraying. Develop by rocking immersion, brushing, scrubbing, etc. Then, if necessary, irradiate ultraviolet rays,
Subsequently, a heat treatment is performed at 100 to 200 ° C. to obtain a printed circuit board having a permanent protective film satisfying various characteristics.

In the above, examples of the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate,
Aqueous solutions of inorganic salts such as sodium metasilicate and potassium metasilicate, and organic amine solutions such as trimethylamine, triethylamine, monomethanolamine, diethanolamine and triethanolamine, and ammonium such as tetramethylammonium hydroxide and tetraethylammonium hydroxide Hydroxide and the like can be mentioned. These can be used alone or in combination of two or more. Further, the temperature can be arbitrarily adjusted between 15 and 45 ° C. A small amount of a surfactant, an antifoaming agent or the like may be mixed in this developer. The photosensitive resin composition of the present invention is completely decomposed in a living body composed of dialkyl glutarate, dialkyl succinate and dialkyl adipate, and has good solubility in the resin by using a mixed solvent (E) that is friendly to the global environment. It has good dispersibility of filler, moderate volatilization rate, and its solid content shows high sensitivity and high resolution, is easy to develop with dilute alkaline aqueous solution, and hardens. The film is also excellent in solder heat resistance, chemical resistance, gold plating resistance, electrolytic corrosion resistance, and the like.

[0042]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Synthesis of Ethylenically Unsaturated Group-Containing Polycarboxylic Acid Resin (A)) Synthesis Example 1 DBE (trade name: mixed solvent manufactured by DuPont, constituent ratio: dimethyl glutarate) 55 to 65 as a reaction solvent in a 2 liter flask % By weight, dimethyl succinate 15-25
% By weight, 10 to 25% by weight of dimethyl adipate)
18.44 g, NER-7403 (epoxy resin manufactured by Nippon Kayaku, a reaction product of bisphenol-F type epoxy resin and epichlorohydrin, epoxy equivalent having 29 or more epoxy resins: 297.8 g) as an epoxy resin having two or more epoxy groups in a molecule.
/ Equivalent) 381.44 g and acrylic acid 92.30
g, 0.30 g of 2-methylhydroquinone as a thermal polymerization inhibitor and 1.78 g of triphenylphosphine as a reaction catalyst were reacted at 98 ° C. for 24 hours. After the reaction was completed, 231.56 g of DBE and 176.26 of tetrahydrophthalic anhydride as a polybasic anhydride were added to this solution.
g, 0.38 g of 2-methylhydroquinone as a thermal polymerization inhibitor was charged and reacted at 95 ° C. for 4 hours to obtain a solution containing an ethylenically unsaturated group-containing polycarboxylic acid resin (referred to as A-1). The concentration of the resin solution was about 65% by weight, and there was no insoluble matter. The acid value of the solid content is 100 mg KO
H / g.

Synthesis Example 2 RHODIAS was used as a reaction solvent in a two-liter flask.
118.44 g of OLV RPDE (trade name: mixed solvent manufactured by Rhone Poulin Nichika, composition ratio: 57 to 63% by weight of dimethyl glutarate, 21 to 27% by weight of dimethyl succinate, 12 to 20% by weight of dimethyl adipate), molecule As an epoxy resin having two or more epoxy groups therein, EPPN-503 (Nippon Kayaku epoxy resin, epoxy resin of polycondensate of phenol and hydroxybenzaldehyde, epoxy equivalent: 180.0 g / equivalent) was 33.
8.30 g, 135.44 g of acrylic acid, 0.30 g of 2-methylhydroquinone as a thermal polymerization inhibitor, and 1.78 g of triphenylphosphine as a reaction catalyst were reacted at 98 ° C. for 5 hours. After the reaction, 17.63 g of tetrahydrophthalic anhydride was added as a polybasic acid anhydride, and the reaction was further continued at 98 ° C. for 20 hours. After the completion of the reaction, 23 parts of RHODIASOLV RPDE was added to this solution.
1.56 g, tetrahydrophthalic anhydride 158.63
g, 0.38 g of 2-methylhydroquinone as a thermal polymerization inhibitor was charged and reacted at 95 ° C. for 4 hours to obtain a solution containing an ethylenically unsaturated group-containing polycarboxylic acid resin (referred to as A-2). The concentration of the resin solution was about 65% by weight, and there was no insoluble matter. The acid value of the solid content is 100 mg KO
H / g.

Comparative Resin Synthesis Example 1 A solution containing an ethylenically unsaturated group-containing polycarboxylic acid resin (for comparison) was prepared in the same manner as in Example 2 except that diethylene glycol monoethyl ether acetate was used as a reaction solvent. Resin). The concentration of the resin solution was about 65% by weight. The solid content acid value is 100 mg
KOH / g.

Examples 1 to 3 Each component was blended according to the blending composition shown in Table 1 (the numerical values are parts by weight) and kneaded in one, two and three passes on a three-roll mill to obtain the photosensitive resin of the present invention. A composition was obtained. At this time, the dispersibility was measured with a grain gauge for each pass. This was applied to the entire surface of the copper-clad laminate, which had been patterned to a thickness of 15 to 25 μm, using a 100-mesh screen by a screen printing method.
After drying for 10, 20, and 30 minutes in a hot air dryer at ℃, tackiness was observed by a finger touch test. Next, a negative film having a resist pattern was brought into close contact with the coating film, and irradiated with ultraviolet rays (exposure amount: 500 mJ / cm) using an ultraviolet exposure device (Oak Seisakusho, Model HMW-680GW).
² ). Next, with a 1% aqueous solution of sodium carbonate for 60 seconds,
Development was performed with a spray pressure of 1.0 kg / cm ² , and unexposed portions were dissolved and removed. The obtained product was evaluated for developability and photosensitivity as described below. Then 150 ° C
Was heated and cured for 60 minutes using a hot air dryer, and the test piece having the obtained cured film was tested for adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, and gold plating resistance as described below. . Table 2 shows the results. In addition, the test method and the evaluation method are as follows.

(Dispersibility) The following evaluation criteria were used.・: Lump remains. ×: Uniformly dispersed.

(Tackiness) The following evaluation criteria were used. ○ ・ ・ ・ ・ No tack. Δ: There is a slight tack. X: There is tack (solvent remains).

(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.

(Photosensitivity) A step tablet (manufactured by Kodak Co., Ltd.) was brought into close contact with the dried coating film, and the integrated
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 1.0 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

(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 × ・ ・ ・ ・ Peeled

(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 abnormality in the appearance of the coating film and no blistering or peeling × ・ ・ ・ ・ Pattern with blistering or peeling

(Acid Resistance) A test piece is immersed in a 10% by weight aqueous hydrochloric acid solution 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 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 McDermitt 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 (manufactured by Meltex, an aqueous solution of 15 vol% of Aurolectroles UP and 3 vol% of potassium gold cyanide, pH 6), electroless gold plating was performed, followed by rinsing with water, and further immersion in warm water of 60 ° C. Immersed for a minute, then 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. ×: Peeled.

Table 1 Example Comparative Example 1 2 3 1 Carboxylic resin (A) A-1 40.0 45.8 A-2 40.0 Comparative resin 40.0 Mixed solvent (E) * 0 (26.0) (29.8) (26.0) (0 ) Photopolymerization initiator (C) Irgacure 907 * 1 3.8 4.3 3.8 3.8 DETX-S * 2 0.4 0.4 0.4 0.4 Photocrosslinking agent (B) DPHA * 3 7.5 4.3 7.5 7.5 TMPTA * 4 4.3 Epoxy resin (D) TEPIC- S * 5 3.8 3.8 YX-4000 * 6 3.8 8.6 7.4 3.8 Curing accelerator Melamine 1.1 1.3 1.1 1.1 Additive BYK-354 * 7 0.8 0.8 0.8 0.8 BYK-057 * 8 0.8 0.8 0.8 0.8 Filler Barium sulfate 17.6 8.6 13.0 17.6 Silica 7.5 5.2 12.0 7.5 Talc 0.8 0.9 1.0 0.8 Phthalocyanine green 0.6 0.7 0.7 0.6 Solvent Mixed solvent (E) 11 0.5 11.0 PGMA * 9 13.5 Carbitol acetate 1.0 Solvent naphtha 10.0

(Note) * 0 Mixed solvent (E) contained in the ethylenically unsaturated group-containing polycarboxylic acid resin solution (A) obtained in the synthesis example.
* 1 Ciba-Geigy: 2-methyl- (4- (methylthio) phenyl) -2-morpholino-1-propane * 2 Nippon Kayaku: 2,4-diethylthioxanthone * 3 Nippon Kayaku: dipentaerythritol Hexaacrylate * 4 Nippon Kayaku: Trimethylolpropane triacrylate * 5 Nissan Chemical Industries: Tris (2,3-epoxypropyl) isocyanurate * 6 Yuka Shell: 3,3 ', 5,5'-tetra Methyl-4,4'-di (2,3-epoxypropyloxy) biphenyl * 7 Made by Big Chemie: Leveling agent * 8 Made by Big Chemie: Antifoaming agent * 9 Propylene glycol monomethyl ether acetate

Table 2 Example Comparative example 1 2 3 1 Evaluation item Dispersibility After 1 pass ○ ○ ○ × After 2 passes ○ ○ ○ × After 3 passes ○ ○ ○ ○ Tackiness 10 minutes △ △ ○ × 20 minutes ○ ○ ○ △ 30 minutes ○ ○ ○ ○ Developability ○ ○ ○ ○ Photosensitivity ○ ○ ○ △ Adhesion ○ ○ ○ ○ Pencil hardness 8H 8H 8H 8H Solvent resistance ○ ○ ○ △ Acid resistance ○ ○ ○ ○ Heat resistance ○ ○ ○ ○ Gold plating resistance ○ ○ ○ △

As is clear from the results shown in Table 2, the photosensitive resin composition of the present invention containing the mixed solvent (E) comprising dialkyl glutarate, dialkyl succinate and dialkyl adipate is particularly useful in dispersibility and drying property. The cured product is excellent in hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance and the like.

[0061]

The mixed solvent comprising dialkyl glutarate, dialkyl succinate and dialkyl adipate (E)
The photosensitive resin composition of the present invention having excellent dispersibility can shorten the kneading and dispersing step for obtaining the composition, and the mixed solvent (E) further comprises When applied on top, it has an appropriate volatilization rate, so it is easy to obtain a uniform film thickness, the drying process can be shortened, and further, it is selectively exposed to ultraviolet light through the film on which the pattern is formed, and then the unexposed part is exposed. In the development of solder resist pattern for development, it has excellent developability and photosensitivity, and the obtained cured product has satisfactory adhesiveness, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance, etc. It is particularly suitable for a liquid solder resist ink composition for a printed wiring board to be subjected to gold plating.

Claims (9)

[Claims] 1. A photosensitive resin composition for producing an electronic circuit board, comprising a mixed solvent (E) comprising a dialkyl glutarate, a dialkyl succinate and a dialkyl adipate. 2. The photosensitive composition according to claim 1, comprising an ethylenically unsaturated group-containing polycarboxylic acid resin (A), a photocrosslinking agent (B), a photopolymerization initiator (C) and an epoxy resin (D). Resin composition 3. The ratio of each component constituting the mixed solvent (E) is 50 to 70% by weight of dialkyl glutarate, 10 to 30% by weight of dialkyl succinate, and 5 to 30% by weight of dialkyl adipate.
The photosensitive resin composition according to claim 1, wherein the content is from 30 to 30% by weight. 4. The photosensitive resin composition according to claim 1, wherein the dialkyl glutarate is dimethyl glutarate. 5. The photosensitive resin composition according to claim 1, wherein the dialkyl succinate is dimethyl succinate. 6. The photosensitive resin composition according to claim 1, wherein the dialkyl adipate is dimethyl adipate. 7. The polycarboxylic acid resin containing an ethylenically unsaturated group (A) is a polybasic acid anhydride adduct (a) of an epoxy (meth) acrylate resin.
The photosensitive resin composition described in 8. A cured product of the photosensitive resin composition according to any one of claims 1 to 7. 9. A printed circuit board having the cured product layer according to claim 8.