JPH07157703A - Resist ink composition and its cured material - Google Patents

Abstract

PURPOSE:To provide the resist ink composition containing an unsaturated group- containing polycarboxylic acid resin, a photopolymerization initiator, a diluent, a curing component and aluminium hydroxide, capable of forming a cured material excellent in adhesion, solder reflow heat resistance, etc., and capable of development by using an aqueous dilute alkali solution. CONSTITUTION:This resist ink composition contains (A) preferably 10 to 80 wt.% unsaturated group-containing polycarboxylic acid resin [acid value is preferably 40 to 100, especially preferably 50 to 85 (mgKOH/g)], (B) preferably 0.5 to 20 wt.% photopolymerization initiator (e.g. benzoin or acetophenone), (C) preferably 5 to 80wt.% diluent [e.g. ethyl methyl ketone, toluene or 2- hydroxyethyl (meth)acrylate], (D) preferably 1 to 50wt.% curing component (e.g. an epoxy compound), (E) preferably 20 to 50wt.% aluminium hydroxide preferably having 0.1 to 20mum particle size and (F) preferably 0 to 60wt.% fine particles of tetrafluoroethylene resin as an arbitrary component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is capable of developing with a dilute alkaline aqueous solution which can be used as a solder resist or an electroless plating resist in the production of printed wiring boards, and the cured product has improved adhesion, solder heat resistance and the like. The present invention relates to a resist ink composition which is excellent and can give a clear mark by irradiating the surface of a cured product with a laser beam, and a cured product thereof.

[0002]

2. Description of the Related Art In recent years, ultraviolet ray curable compositions have been widely used in various fields for reasons such as resource saving, energy saving, workability improvement and productivity improvement. In the field of printed wiring board processing, for the same reason, various inks such as solder resist inks and marking inks have been transferred from conventional thermosetting compositions to ultraviolet curable compositions.

[0003]

Although a screen printing method has been often used as a method for forming a resist pattern on a printed wiring board, when such a screen printing method is used, in many cases, bleeding, bleeding during printing, Or, development such as sagging occurs, which makes it impossible to cope with the recent high density of printed wiring boards and surface mounting of components. In order to solve these problems, a liquid photo solder resist that can be developed with a dilute alkaline aqueous solution has been developed. However, these cured products of liquid photosolder resist cannot give a clear mark by irradiation with a laser beam, and therefore, a marking ink must be used to mark characters and symbols, which is a process problem. .

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, they can be developed with a dilute alkaline aqueous solution and are excellent in adhesion, solder heat resistance, electroless gold plating resistance and the like. We have succeeded in providing a resist ink composition which gives a cured product and can give a clear mark by irradiation with a laser beam. That is, in the present invention, the unsaturated group-containing polycarboxylic acid resin (A), the photopolymerization initiator (B), the diluent (C), the curing component (D) and the aluminum hydroxide (E), and the tetracarboxylic acid The present invention relates to a resist ink composition containing a fine particle of a fluoroethylene resin (F) and a cured product thereof.

Specific examples of the unsaturated group-containing polycarboxylic acid resin (A) used in the present invention include, for example, an epoxy compound (a) having at least two epoxy groups in one molecule and an unsaturated group-containing resin. A compound obtained by reacting the reaction product (I) obtained by reacting a monocarboxylic acid (b) with a polybasic acid anhydride (c), or the reaction product (I) with the polybasic acid anhydride (c). And an unsaturated group-containing monoisocyanate (d) are reacted with each other.

Specific examples of the epoxy compound (a) having at least two epoxy groups in one molecule include, for example, novolac type epoxy resins (for example, phenol,
Those obtained by reacting novolaks obtained by reacting phenols such as cresol, halogenated phenols and alkylphenols with formaldehyde under an acidic catalyst with epichlorohydrin and / or methylepichlorohydrin. Examples of commercially available products include Nippon Kayaku Co., Ltd., EOCN-103, EOCN-104S, and E.
OCN-1020, EOCN-1027, EPPN-2
01, BREN-S; Dow Chemical Co., DEN-4
31, DEN-439; Dainippon Ink and Chemicals, Inc.
Made, N-730, N-770, N-865, N-66
5, N-673, VH-4150 and the like. ), A bisphenol type epoxy resin (for example, those obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A with epichlorohydrin and / or methylepichlorohydrin, and diglycidyl ether of biphenol A). Those obtained by reacting the condensate of the bisphenols with epichlorohydrin and / or methylepichlorohydrin, etc. Commercially available products are Yuka Shell Co., Ltd.
Manufactured by Epicoat 1004, Epicoat 1002; manufactured by Dow Chemical Co., DER-330, DER-337 and the like. ),
Trisphenol methane type epoxy resin (for example, those obtained by reacting trichlorophenol methane, triscresol methane and the like with epichlorohydrin and / or methyl epichlorohydrin. Commercially available products thereof are EPPN- manufactured by Nippon Kayaku Co., Ltd. 501, EPPN-502
etc. ) Tris (2,3-epoxypropyl) isocyanurate, biphenyl diglycidyl ether, others, Daicel Chemical Industry Co., Ltd., Celoxide 2021; Mitsui Petrochemical Industry Co., Ltd., Epomic VG-3101: oiled shell epoxy ( Co., Ltd., E-1031S; Mitsubishi Gas Chemical Co., Inc., TETRAD-X, TETRAD-C;
Aliphatic, amino group-containing epoxy resins such as EPB-13 and EPB-27 manufactured by Nippon Soda Co., Ltd., copolymer type epoxy resins (for example, copolymers of glycidyl methacrylate and styrene, glycidyl methacrylate, styrene and methyl methacrylate). Manufactured by NOF CORPORATION, a copolymer of C
P-50M, CP-50S, or a copolymer of glycidyl methacrylate and cyclohexylmaleimide, etc.)
Alternatively, an epoxy resin having a special structure may be used. Particularly preferred are, for example, cresol / novolak type epoxy resin and phenol / novolak type epoxy resin.

Next, specific examples of the unsaturated group-containing monocarboxylic acid (b) include, for example, acrylic acid, a dimer of acrylic acid, methacrylic acid, a saturated or unsaturated dibasic acid anhydride, and one molecule. (Meth) acrylates having one hydroxyl group therein, or half-esters which are reaction products of saturated or unsaturated dibasic acids and unsaturated group-containing monoglycidyl compounds, for example, succinic anhydride, maleic anhydride, Saturated or unsaturated dibasic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. and hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate,
Half-esters or saturated or unsaturated dibasic acids (for example, succinic acid) obtained by reacting equimolar amounts of (meth) acrylates having one hydroxyl group in one molecule such as hydroxybutyl (meth) acrylate. , Maleic acid, adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, itaconic acid, etc.) and unsaturated group-containing monoglycidyl compounds (eg, glycidyl (meth) acrylate,

[0008]

[Chemical 1]

Etc. Can be used alone or as a mixture thereof. Particularly preferred is acrylic acid. In the reaction of the epoxy compound (a) with the unsaturated group-containing monocarboxylic acid (b), about 0 equivalent of the unsaturated group-containing monocarboxylic acid (b) relative to 1 equivalent of the epoxy group of the epoxy compound (a). ．
The reaction is preferably carried out in a ratio of 8 to 1.5 mol, particularly preferably in a ratio of about 0.9 to 1.1 mol. During the reaction, as a diluent, 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 , Butyl acetate, butyl cellosolve acetate, esters such as carbitol acetate, aliphatic hydrocarbons such as octane and decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, organic solvents such as petroleum solvents such as solvent naphtha, or Carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (hydroxyethyl) isocyanurate Tri (meth) acrylate, preferably used reactive monomers such as dipentaerythritol hexa (meth) acrylate. Further, a catalyst for promoting the reaction (eg, triethylamine, benzyldimethylamine, methyltriethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, chromium octanoate, zirconium octanoate). Etc.) is preferably used, and the amount of the catalyst used is preferably 0.1 to 10% by weight with respect to the reaction raw material mixture. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc.), and the amount thereof is preferably relative to the reaction raw material mixture. Is 0.01 to 1% by weight. The reaction temperature is preferably 60 to 150 ° C. The reaction time is preferably 5 to 60 hours. In this way, the reaction product (I) can be obtained.

Next, the reaction product (I) and polybasic acid anhydride (C) (for example, maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride). Acid, methylendomethylenetetrahydrophthalic anhydride, trimellitic acid, pyromellitic acid and the like, particularly preferably, for example, the reaction of tetrahydrophthalic anhydride, succinic anhydride and the like, the hydroxyl group in the reaction product (I), It is preferable to react 0.1 to 0.9 equivalent of the polybasic acid anhydride (C) per 1 equivalent of hydroxyl group, the reaction temperature is preferably 60 to 150 ° C., and the reaction time is preferably 1 to 10 hours. Specific examples of the saturated group-containing monoisocyanate (d) include, for example,

[0011]

[Chemical 2]

[0012]

[Chemical 3]

Reacting an organic diisocyanate (for example, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc.) with the above-mentioned (meth) acrylates having one hydroxyl group in one molecule in an approximately equimolar amount; And the like. The reaction of the reaction product (I) with the polybasic acid anhydride (c) and the unsaturated group-containing monoisocyanate (d) is performed by reacting the reaction product (I) with the polybasic acid anhydride (c), It is preferable to react the unsaturated group-containing monoisocyanate (d). The reaction between the reactant (I) and the polybasic acid anhydride (c) can be carried out by carrying out as described above. Then, with respect to the hydroxyl group in the reaction product of the reaction product (I) and the polybasic acid anhydride (c), the unsaturated group-containing monoisocyanate (d) is reacted in an amount of 0.05 to 0.5 equivalent per 1 equivalent of the hydroxyl group. Preferably. The reaction temperature is preferably 60 to 100 ° C. It is preferable to add a small amount of catalyst (for example, dibutyltin laurate) during the reaction, and the reaction time is 5 to 1
5 hours is preferred.

The acid value (mgKOH / g) of the unsaturated group-containing polycarboxylic acid resin (A) thus obtained is 40.
-100 is preferable and 50-85 is especially preferable. The amount of the unsaturated group-containing polycarboxylic acid resin (A) contained in the composition of the present invention is preferably 10 to 80% by weight, and particularly preferably 15 to 60% by weight in the composition.

Next, specific examples of the photopolymerization initiator (B) include, for example, benzoin, benzoin methyl ether,
Benzoins such as benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl- 1
-[4- (Methylthio) phenyl] -2-morpholinopropan-1-one, acetophenones such as N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1 -Chloroanthraquinone, 2-amylanthraquinone, anthraquinones such as 2-aminoanthraquinone, 2,4-dimethylthioxanthone,
2,4-Diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and other thioxanthones, acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals, benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4, Benzophenones such as 4'-bisdiethylaminobenzophenone, Michler's ketone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,
There are 4,6-trimethylpenzoyldiphenylphosphine oxide and the like, which can be used alone or in combination of two or more kinds. Furthermore, with the photopolymerization initiator (B), N,
N-dimethylaminobenzoic acid ethyl ester, N, N-
Dimethylaminobenzoic acid isoamyl ester, benzyl 4-dimethylaminobenzoate, triethylamine,
Photosensitizers such as tertiary amines such as triethanolamine can be used alone or in combination of two or more kinds.

The preferred combination is 2-methyl-1- [4
-(Methylthio) phenyl] -2-morpholinopropan-1-one (Ciba Geigy, Irgacure 907) and 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd., Kayacure DETX) and 2-isopropyl Combination with thioxanthone, 4-benzoyl-4'-methyldiphenyl sulfide and the like. The proportion of the photopolymerization initiator (B) used is 0.5 to 20 in the composition of the present invention.
Weight% is preferred, and especially preferred is 1 to 10 weight%.

Next, as a specific example of the diluent (C), for example, an organic solvent and / or a photopolymerizable monomer can be used.
Typical organic solvents include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol and propylene glycol. Monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers, ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate and other esters, ethanol, propanol, ethylene Glycol,
Alcohols such as propylene glycol, aliphatic hydrocarbons such as octane and decane, petroleum ether, petroleum naphtha,
Examples thereof include petroleum-based solvents such as hydrogenated petroleum naphtha and solvent naphtha.

On the other hand, typical examples of the photopolymerizable monomer include 2-hydroxyethyl (meth) acrylate,
Hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, mono or di (meth) acrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, N, N-dimethyl (meth) acrylamide. , (Meth) acrylamides such as N-methylol (meth) acrylamide, aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane , Dipentaerythritol, tris-hydroxyethyl isocyanurate, and other polyhydric alcohols, or their polyhydric (meth) acrylates of ethylene oxide or propylene oxide adducts. , Phenoxyethyl (meth) acrylate, polyethoxydi (meth) acrylate of bisphenol A, ethylene oxide or propylene oxide adduct (meth) acrylate, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether , (Meth) acrylates of glycidyl ethers such as triglycidyl isocyanurate, and melamine (meth) acrylate.

The diluent (C) is used alone or as a mixture of two or more kinds, and the amount of the diluent (C) contained in the composition of the present invention is preferably 5 to 80% by weight in the composition. And particularly preferably 10 to 70% by weight. The purpose of use of the diluent (C) is to use a photopolymerizable monomer,
While diluting the component (A) to make it easy to apply,
It enhances photopolymerizability, and in the case of organic solvents,
This is because the component (A) is dissolved and diluted so that it is applied as a liquid and then dried to form a film. Therefore, either a contact method or a non-contact exposure method in which the photomask is brought into contact with the coating film is used depending on the diluent used.

Next, as the curing component (D) used in the present invention, those which do not have an unsaturated double bond and which themselves cure by heat, ultraviolet rays, etc., and the main component in the composition of the present invention The component (A), which is a component, reacts with a hydroxyl group, a carboxyl group, or the like by heat, ultraviolet rays, or the like. In particular,
For example, an epoxy compound having one or more epoxy groups in one molecule (for example, Yuka Shell Co., Ltd., Epicoat 1009, 1031, Dainippon Ink and Chemicals, Inc.,
Epicron N-3050, N-7050, Dow Chemical Co., DER-642U, DER-673MF and other bisphenol A type epoxy resins, Tohto Kasei Co., Ltd., ST
-2004, ST-2007 and other hydrogenated bisphenol A
Type epoxy resin, Toto Kasei Co., Ltd., YDF-200
4, bisphenol F type epoxy resin such as YDF-2007, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., SR-BBS, SR-T
BA-400, manufactured by Tohto Kasei Co., Ltd., YDB-600, Y
Brominated bisphenol A type epoxy resin such as DB-715, manufactured by Nippon Kayaku Co., Ltd., EPPN-201, EOCN-
Novolak type epoxy resins such as 103, EOCN-1020 and BREN, manufactured by Dainippon Ink and Chemicals, Inc., novolac type epoxy resin of bisphenol A such as Epicron N-880, manufactured by Yuka Shell Co., Ltd., YL-931, Y
Amino group-containing epoxy resin such as L-933, Dainippon Ink and Chemicals Incorporated, rubber modified epoxy resin such as Epiclon TSR-601, Nippon Kayaku Co., Ltd., EBPS-2
00, manufactured by Dainippon Ink and Chemicals, Inc., Epicron EX
A-1514 and other bisphenol S type epoxy resins, NOF CORPORATION, diglycidyl terephthalate such as Blemmer DGT, Nissan Chemical Co., Ltd., triglycidyl isocyanurate such as TEPIC, Yuka Shell Co., Ltd., Y
Bixylenol type epoxy resin such as X-4000, Yuka Shell Co., Ltd., biphenol type epoxy resin such as YL-6056, Daicel Chemical Industries Ltd., alicyclic epoxy resin such as Celoxide 2021, etc.), melamine Derivatives (eg, hexamethoxymelamine, hexabutoxylated melamine, condensed hexamethoxymelamine, etc.), urea compounds (eg, dimethylolurea, etc.), bisphenol A compounds (eg, tetramethylol-bisphenol A, etc.), oxazoline compounds, etc. Can be mentioned.

The purpose of using the curing component (D) is to improve various properties as a solder resist such as adhesion, heat resistance, and plating resistance. The curing component (D)
Are used alone or as a mixture of two or more kinds, and the amount of the curing component (D) contained in the composition of the present invention is 1 in the composition.
˜50% by weight is preferred, and particularly preferred is 3 to 45% by weight.

When an epoxy compound is used in the curing component (D), it is preferable to use an epoxy resin curing agent together in order to further improve the properties such as adhesion, chemical resistance and heat resistance. Specific examples of such an epoxy resin curing agent include 2M manufactured by Shikoku Chemicals Co., Ltd.
Z, 2E4MZ, C ₁₁ Z, C ₁₇ Z, 2PZ, 1B2M
Z, 2MZ-CN, 2E4MZ- CN, C 11 Z-CN,
2PZ-CN, 2PHZ-CN, 2MZ-CNS, 2E
4MZ-CNS, 2PZ-CNS, 2MZ-AZIN
E, 2E4MZ-AZINE, C ₁₁ Z-AZINE, 2
MA-OK, 2P4MHZ, 2PHZ, 2P4BHZ and other imidazole derivatives: acetoguanamine, benzoguanamine and other guanamines: diaminodiphenylmethane,
m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea,
Polyamines such as urea derivatives, melamine and polybasic hydrazides: their organic acid salts and / or epoxy adducts:
Amine complex of boron trifluoride: ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4
Triazine derivatives such as -diamino-6-xylyl-S-triazine: trimethylamine, triethanolamine, N, N-dimethylthiooctylamine, N-benzylmethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) Melamine, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, m
-Tertiary amines such as aminophenol: polyvinylphenol, polyvinylphenol bromide, phenol novolac, polyphenols such as alkylphenol novolac: tributylphosphine, triphenylphosphine, organic phosphines such as tris-2-cyanoethylphosphine: tri-n -Phosphonium salts such as butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride:
Quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride: the above polybasic acid anhydrides: diphenyliodonium tetrafluoroboroate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexa Fluorophosphate, manufactured by Ciba Geigy, Irgacure 261, Asahi Denka Co., Ltd.
Cationic polymerization catalyst such as Optomer SP-170 manufactured by:
Styrene-maleic anhydride resin: Well-known and commonly used curing agents such as equimolar reaction products of phenyl isocyanate and dimethylamine, and organic polyisocyanates such as tolylene diisocyanate and isophorone diisocyanate, and equimolar reaction products, or acceleration of curing. The agents are used alone or in combination of two or more. The amount of the epoxy resin curing agent used is preferably 0.01 to 25 parts by weight, and particularly preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the epoxy compound.

The particle size of aluminum hydroxide used in the present invention is preferably in the range of 0.1 to 20 μ, and particularly preferably 0.3 to 10 μ. The amount used is preferably 10 to 60% by weight in the composition, particularly preferably 20 to
It is 50% by weight. If the content is less than 10% by weight, clear contrast due to laser beam irradiation cannot be obtained, and if it exceeds 60% by weight, the physical properties of the ink are poor and there is a problem in use.

The particle size of the fine particles of the tetrafluoroethylene resin (F) used as an optional component in the present invention is 0.1.
Is preferably in the range of .about.20 .mu., Particularly preferably 0.3 to 1.
0 μ. Fine particles of the tetrafluoroethylene resin (F) can obtain a clear contrast by irradiation with a laser beam without being necessarily used in the present invention. However, when the marked cured product is fluxed and then immersed in a solder bath, The sharpness of the marking is better when the tetrafluoroethylene resin fine particles are used. The amount of its use in the composition is preferably 0 to 60% by weight, particularly preferably 10 to 50% by weight. If the content exceeds 60% by weight, the physical properties of the ink may be poor.

The composition of the present invention may further contain, if necessary, an inorganic filler other than the above-mentioned aluminum hydroxide, a conventionally known colorant, a dispersant, a fluidity modifier, a flame retardant, a lubricant, a light stabilizer, Known and commonly used additives such as antioxidants can be used.

Further, known binder resins and polyesters (meth) such as copolymers of ethylenically unsaturated compounds such as acrylic acid esters, polyester resins synthesized from polyhydric alcohols and polybasic acid compounds, etc. ) Photopolymerizable oligomers such as acrylates, polyurethane (meth) acrylates, and epoxy (meth) acrylates can also be used within a range that does not affect various properties as a solder resist.

Water may also be added to reduce the flammability of the composition of the present invention. When adding water,
The carboxyl group of the component (A) has amines such as trimethylamine and triethylamine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, It is preferred that the component (A) is dissolved in water by salt formation with a (meth) acrylate compound having a tertiary amino group such as acryloylmorpholine, N-isopropyl (meth) acrylamide, N-methylolacrylamide. . The composition of the present invention is obtained by blending the blending components preferably in the above proportions and uniformly mixing them with a roll mill or the like.

The resist ink composition of the present invention is cured, for example, as follows to obtain a cured product. That is, a printed wiring board is coated with the composition of the present invention in a film thickness of 10 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 flow coating method to form a coating film. After drying at 60 to 110 ° C., the negative film is brought into direct contact with the coating film (or placed on the coating film without contacting it), and then irradiated with ultraviolet rays to dilute the unexposed portion with a dilute alkaline aqueous solution ( For example, after dissolution removal (development) with 0.5 to 2% sodium carbonate aqueous solution, etc., irradiation with ultraviolet rays and / or heating (for example, 10%) to further improve various physical properties.
0.5 to 1.0 hours at 0 to 200 ° C. ) To obtain a cured film.

[0029]

EXAMPLES The present invention will be described in more detail below with reference to examples. The parts in the synthesis examples are parts by weight. Synthesis example of unsaturated group-containing polycarboxylic acid resin (A) Synthesis example 1 Cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C, epoxy equivalent 220) 2200 parts (10 equivalents) ), Acrylic acid 7
20 parts (10 mol), 4.5 parts of methylhydroquinone,
1107 parts of carbitol acetate and 475 parts of solvent naphtha were charged and heated to 90 ° C. and stirred to dissolve the reaction mixture. Then, the reaction solution was cooled to 60 ° C., charged with 13.5 parts of triphenylphosphine, heated to 100 ° C., reacted for about 32 hours, and had an acid value of 1.1 mgKOH /
g reaction product was obtained. Next, 878.9 parts of tetrahydrophthalic anhydride, 331 parts of carbitol acetate and 142.2 parts of solvent naphtha were charged into this, heated to 95 ° C., reacted for about 6 hours, cooled, and acid value of the solid component. Is 85m
An unsaturated group-containing polycarboxylic acid resin (A-1) having a solid content of 65% of gKOH / g was obtained.

Synthetic Example 2 2200 parts (10 equivalents) of cresol / novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy equivalent 220), acrylic acid 7
20 parts (10 mol), 4.5 parts of methylhydroquinone,
1107 parts of carbitol acetate and 475 parts of solvent naphtha were charged and heated to 90 ° C. and stirred to dissolve the reaction mixture. Then, the reaction solution was cooled to 60 ° C., charged with 13.5 parts of triphenylphosphine, heated to 100 ° C., reacted for about 32 hours, and had an acid value of 1.1 mgKOH /
g of reaction product was obtained. Next, this was charged with 947 parts of tetrahydric phthalic anhydride, 357 parts of carbitol acetate and 153 parts of solvent naphtha, heated to 95 ° C., reacted for about 6 hours, cooled, and the acid value of the solid component was 90 mgKOH /
g product was obtained. Then, 143 parts of isocyanate ethyl methacrylate and 5 parts of carbitol acetate
Charge 3.9 parts and solvent naphtha 23.1 parts 5
The mixture was heated to 0 ° C., reacted for 10 hours, infrared absorption spectrum was measured, and the reaction was terminated by confirming that the isocyanate group had disappeared. The acid value of the solid component was 86.8 mg.
An unsaturated group-containing polycarboxylic acid resin (A-2) having a solid content of KOH / g of 65% was obtained.

Examples 1 to 3 and Comparative Example 1 Resist ink compositions (a) and (b) were blended according to the blending composition shown in Table 1 (numerical values are parts by weight) and kneaded separately with a three-roll mill. (I) 250 g and (b) 70 g were mixed and prepared. This is screen-printed using a 100-mesh polyester screen to a thickness of 20 to 30 μm, and is applied over the entire surface to a patterned copper through-hole printed wiring board, and the coating film is dried at 80 ° C. in a hot air drier. The film is dried for 30 minutes at 37 ° C., a negative film having a resist pattern is brought into close contact with the coating film, and an ultraviolet exposure device (Oak Seisakusho Co., Ltd., model HMW-6
80 GW) was used to irradiate with ultraviolet rays (exposure amount 350
mJ / cm ² ). Then develop with a 1% aqueous sodium carbonate solution for 60 seconds at a spray pressure of 2.0 kg / cm ² ,
The unexposed part was dissolved and removed. After that, heat curing was performed for 40 minutes with a hot air dryer at 150 ° C., and the test piece having the obtained cured film was tested for adhesion, solder heat resistance, and
A laser marking property test was conducted. The results are shown in Table 1. The test method and evaluation method are as follows.

(Adhesion) According to the test method of JIS D 0202, cross-cuts were put on the cured film in a grid pattern, and then the state of peeling after a peeling test with cellophane tape was visually judged. ◎ ・ ・ ・ ・ 100/100 with no peeling ○ ・ ・ ・ ・ 100/100 with a little cross-cut portion △ ・ ・ ・ ・ 50/100 to 90/100 × ・ ・ ・ ・0/100 to 50/100

(Solder Heat Resistance) According to the test method of JIS C 6481, the test piece was immersed in a solder bath at 260 ° C. for 10 seconds 3 times or 2 times to evaluate the change in appearance. (Post-flux resistance) Immersion was performed 3 times for 10 seconds and the change in appearance was evaluated. ○ ・ ・ ・ ・ No change in appearance △ ・ ・ ・ ・ ・ ・ Discoloration of the cured film is observed × ・ ・ ・ ・ Floating, peeling, or solder dip in the cured film Note) Post-flux (rosin type) used: JIS
Use flux according to C 6481.

(Flux resistance for levelers) Immersion was carried out twice for 10 seconds and after immersion in boiling water for 10 minutes, the change in appearance was evaluated. ○ ・ ・ ・ ・ No change in appearance △ ・ ・ ・ ・ Discoloration of cured film is observed × ・ ・ ・ ・ Floating, peeling, and solder dip in cured film Note) Flux for leveler used: manufactured by MEC Co., Ltd. ,
W-121

(Laser Marking Property) A carbon dioxide gas laser (manufactured by Laser Technics BLAZAR6
A 000 type, energy density 3.3 J / cm ² ) was used to irradiate a laser to make white markings, and the sharpness of the markings was compared. Further, the marked cured films were subjected to flux treatment and then the sharpness of the markings when immersed in a solder bath at 260 ° C. was compared. ○ ・ ・ ・ ・ Good △ ・ ・ ・ ・ Slightly bad × ・ ・ ・

[0036]

Table 1 Examples Comparative Examples 1 2 3 1 (a) Unsaturated group-containing polycarboxylic acid resin (A-1) 154 154 154 Unsaturated group-containing polycarboxylic acid resin (A-2) 154 Irgacure 907 12 12 12 12 Kayacure DETX-S 0.5 0.5 0.5 0.5 Carbitol acetate 5 5 5 5 Solvesso 150 5 5 5 5 KAYARAD DPHA 10 10 10 10 Aluminum hydroxide (average particle size 0.3μ) 20 20 54.7 Tetrafluoroethylene resin ( Average particle size 5.5μ) 34.7 34.7 Phthalocyanine green (coloring pigment) 1.8 1.8 1.8 1.8 Aerosil 380 5 5 5 5 Dicyandiamide (epoxy curing agent) 1 1 1 1 Fuselex 54.7 (b) KAYARAD DPHA 10 10 10 10 Carbitol acetate 10 10 10 10 Solvesso 150 5 5 5 5 EOCN-104S 5 5 5 5 TEPIC 20 20 20 20 Aluminum hydroxide (average Diameter 0.3μ) 20 20 20 Barium sulfate 20 Adhesion ○ ○ ○ ○ Solder heat resistance Post flux resistance ○ ○ ○ ○ Leveler flux resistance ○ ○ ○ ○ Laser marking property Immediately after marking ○ ○ ○ × After immersion in solder bath ○ ○ △ ×

Note) Irgacure 907: photopolymerization initiator, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 manufactured by Ciba Geigy
-ON Kayacure DETX-S: Nippon Kayaku Co., Ltd., photopolymerization initiator 2,4-diethylthioxanthone Solvesso 150: Exxon Chemical Co., Ltd., solvent naphtha KAYARAD DPHA: Nippon Kayaku Co., Ltd. dipentaerythritol Hexa and pentaacrylate mixture Aerosil 380: Nippon Aerosil Co., Ltd., anhydrous silica Fuse Rex: Tatsumori Co., Ltd., fused silica EOCN-104S: Nippon Kayaku Co., o-cresol novolac epoxy resin TEPIC : Nissan Chemical Co., Ltd., triglycidyl ether isocyanurate

As is clear from the evaluation results in Table 1, the cured product of the resist ink composition of the present invention is sufficiently satisfactory in adhesion and solder heat resistance, and is also excellent in laser marking property. Is clear.

[0039]

INDUSTRIAL APPLICABILITY The resist ink composition of the present invention can be developed with a dilute aqueous alkaline solution in the formation of a solder resist pattern by developing an unexposed portion, and the obtained cured product has adhesiveness and solder heat resistance. And the like, is excellent in laser marking property, and is particularly suitable for a liquid solder resist ink composition.

Claims (2)

[Claims] 1. An unsaturated group-containing polycarboxylic acid resin (A),
A resist ink containing a photopolymerization initiator (B), a diluent (C), a curing component (D) and an aluminum hydroxide (E), and as an optional component, fine particles of a tetrafluoroethylene resin (F). Composition. 2. A cured product of the resist ink composition according to claim 1.