JPH07146553A - Photo solder resist composition - Google Patents

Abstract

PURPOSE:To obtain an alkali-developable photo solder resist suitable for use in a process for producing a printed circuit board. CONSTITUTION:This photo solder resist compsn. contains a product obtd. by bringing a polymer of unsatd. monocarboxylic acid or a copolymer of the acid with other ethylenically unsatd. compd. into partial esterification with radical polymerizable monohydric alcohol. This compsn. has superior characteristics such as resistance to chemicals, solvents, water, moisture, alkali, water-soluble flux, etc., and ensures a considerably prolonged usable time after two packs are mixed. It can be allowed to stand for a considerably prolonged time after prebaking and the work efficiency of a photo solder resist is enhanced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photo solder resist which is preferably used in a printed wiring board manufacturing process and the like. Specifically, a photo solder that forms a pattern by irradiation with radiation such as ultraviolet rays and exhibits excellent heat resistance, chemical resistance, water resistance, moisture resistance, solvent resistance and electrical insulation after development with a weak alkaline aqueous solution. The present invention relates to a resist composition.

[0002]

2. Description of the Related Art Solder resists are indispensable materials in printed wiring board manufacturing as a protective film for preventing solder from adhering to unnecessary portions in a soldering process and as a permanent mask. Conventionally, a thermosetting type resist is often used as a solder resist, and a method of printing this by a screen printing method has been generally used. However, with the recent increase in the density of wiring on a printed wiring board, the screen printing method is used. However, there is a limit in resolution, and photo solder resists, which are pattern-formed by a photographic method, are widely used. Among them, the alkaline developing type, which can be developed with a weak alkaline solution such as a sodium carbonate solution, has become the main stream from the viewpoint of work environment protection and global environment protection. As such a thing, the thing etc. which are disclosed by Unexamined-Japanese-Patent No. 63-205649 and Unexamined-Japanese-Patent No. 2-023351 are known.

The alkali-development type photo solder resist does not use an organic solvent for development so that there is no fear of environmental pollution and the influence on the human body is reduced, but there is still a problem in terms of durability. That is, the chemical resistance, solvent resistance, water resistance, moisture resistance, alkali resistance, etc. are inferior to those of the conventional thermosetting type and solvent developing type by the screen printing method. This is because the alkali-development-type photo solder resist is mainly composed of one having a hydrophilic group in order to make it alkali-developable. This is to reduce the adhesiveness of. Therefore, the alkali-development-type photo solder resist is required to have high adhesion to the substrate.

In the photo solder resist, improvement of workability is also an important issue. It is difficult to use the conventional alkali development type photo solder resist as a one-component type in order to maintain the above resistance, and the two-component mixing type is mainly used. In the case of a two-liquid mixing type, it is more preferable that the pot life after mixing, that is, the pot life is long, but the conventional product cannot be said to be sufficiently satisfactory in this respect, and development failure occurs with the passage of time, Deterioration of characteristics occurs.

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that a partial ester of a polymer or copolymer of unsaturated monocarboxylic acid with a radically polymerizable monohydric alcohol. The inventors have found that a photo solder resist composition containing a compound has excellent adhesion to a substrate and has a long pot life, and has reached the present invention.

[0006]

The present invention is characterized in that it comprises a partially esterified product of a radically polymerizable monohydric alcohol of a polymer of an unsaturated monocarboxylic acid or a copolymer with another ethylenically unsaturated compound. A photo solder resist composition is provided.

In the present invention, (A) a partially esterified product of a polymer of an unsaturated carboxylic acid or a copolymer with another ethylenically unsaturated compound by a radical-polymerizable monohydric alcohol is an active energy ray-curable resin, The portion selectively irradiated with active light such as ultraviolet rays, electron beams, and X-rays becomes an insoluble three-dimensional crosslinked product due to the addition reaction of the unsaturated double bond. On the other hand, the portion not irradiated with the actinic light is in a state of maintaining alkali solubility due to the presence of the carboxyl group, and an image is formed by developing with an alkali solution. (A) is used in the range of 20 to 100% by weight in the photo solder resist composition.

Unsaturated monocarboxylic acids include (meth)
Acrylic acid, crotonic acid, β-styryl acrylic acid, β
Examples thereof include, but are not limited to, furfuryl acrylic acid, cinnamic acid, α-cyanocinnamic acid and the like. Further, these may be polymerized alone, or may be copolymerized by combining two or more kinds. The unsaturated monocarboxylic acid may be copolymerized with other ethylenically unsaturated compounds such as acrylic monomers and vinyl monomers.

Examples of acrylic monomers include, but are not limited to, (meth) acrylic acid alkyl ester, (meth) acrylic acid hydroxyalkyl ester, acrylamide, alkylated acrylamide, alkylolated acrylamide, and acrylonitrile. is not. Examples of vinyl monomers include ethylene, propylene, n-butene, isobutene, butadiene, α-olefin, vinyl chloride, isoprene, chloroprene, styrene, α-alkylstyrene, ring-substituted styrene, alkyl vinyl ether, vinyl acetate, allyl alcohol, and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more.

As the polymerizable monohydric alcohol, hydroxyalkyl (meth) acrylate, allyl alcohol,
Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polycaprolactone mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane (meth) acrylate, neopentyl glycol mono (meth) acrylate, 1 , 6-Hexanediol mono (meth) acrylate, tetramethylolmethane tri (meth) acrylate, mono (2- (meth) acryloyloxyethyl) acid phosphate, di (2- (meth) acryloyloxyethyl) acid phosphate , Glycerol di (meth) acrylate, glycerol mono (meth) acrylate and the like, but are not limited thereto.

Examples of the method for obtaining (A) include a method in which a radical-polymerizable monohydric alcohol is reacted with a polymer or copolymer of a precursor unsaturated monocarboxylic acid by condensation. As the reaction catalyst for carrying out the condensation reaction, any of an acid catalyst, a basic catalyst and a Lewis acid catalyst may be used. It is necessary to keep the reaction temperature within the range where radical reaction does not occur, and it is about 50-200.
C is preferred. Further, it is preferable to add an appropriate amount of an azeotropic solvent and attach a trap to perform an operation of removing the desorbed water. Furthermore, it is also preferable to add an appropriate amount of a polymerization inhibitor or blow air.

The amount of the radical-polymerizable monohydric alcohol used is preferably in the range of 0.1 to 0.9 equivalents with respect to the carboxylic acid component of the precursor polymer or copolymer. 0.1
If it is less than the equivalent, curability with active energy rays becomes insufficient, and if it exceeds 0.9 equivalent, the solubility in an alkali developing solution, that is, developability becomes poor. The photo solder resist composition of the present invention further enhances the adhesion between the substrate and the film, and has solvent resistance, chemical resistance, water-soluble flux resistance, boiling resistance, plating resistance, moisture resistance, and electrolytic corrosion resistance. The silane coupling agent (B) can be used in the range that does not reduce workability, that is, in the range of 0 to 5% by weight in the photo solder resist composition, for the purpose of improving the above.

As the silane coupling agent (B), an alkoxysilyl group, a chlorosilyl group, a first functional group,
Those having one or more functional groups selected from aminosilyl groups and one or more functional groups selected from vinyl groups, amino groups, mercapto groups, epoxy groups, and (meth) acryloyl groups as the second functional groups. Among them, those in which the second functional group is a mercapto group or an epoxy group are particularly preferable. The action of (B) is that a functional group such as an alkoxysilyl group, a chlorosilyl group, an aminosilyl group, which is the first functional group, reacts with an active hydroxyl group on the metal surface which is the base material,
Furthermore, since the second functional group reacts with the carboxyl group and the polymerizable unsaturated group of the component (A), it is to improve the adhesion between the metal base material and the film.

Specific examples of the silane coupling agent (B) include vinyltrichlorosilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane and N-.
(Β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, Examples thereof include, but are not limited to, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and the like. These may be used alone or in combination of two or more.

In the photo solder resist composition of the present invention, in addition to the above components (A) and (B), the physical properties are improved,
For the purpose of improving workability and storage stability, the following components (C) to (H) can be used, if necessary. From (C) a photopolymerization initiator and / or a photopolymerization accelerator, (D) a compound having one or more epoxy groups, (E) a latent thermosetting agent, a thermosetting agent solid at room temperature, a thermosetting accelerator One or more selected (F) Ethylenically unsaturated compound having no epoxy group (G) One or more selected from organic solvent and water (H) Other additives

The (C) photopolymerization initiator and / or the photopolymerization accelerator is necessary when the active energy ray used for photopolymerization is ultraviolet light, and is 0 to 20 in the photosolder resist composition. It can be used in the range of% by weight. As the photopolymerization initiator, benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,2 -Diethoxyacetophenone, 2,4-diethylthioxanthone and the like, and examples of the photopolymerization accelerator include isoamyl p-dimethylbenzoate, 4,4-bis (diethylamino) benzophenone and dimethylethanolamine.

The compound (D) having one or more epoxy groups is contained in the photo solder resist composition in an amount of 0 to 50 in order to improve performances such as film strength, heat resistance, durability, chemical resistance and environmental resistance. It can be used in the range of% by weight. As such, one or more selected from triglycidyl isocyanurate, hydroquinone diglycidyl ether, bisphenol diglycidyl ether, cresol novolac type epoxy resin and phenol novolac type epoxy resin are reactive,
Most preferred in terms of physical properties and storage stability. As the cresol novolac type epoxy resin, "Epiclon N-695" manufactured by Dainippon Ink and Chemicals, Inc., as the phenol novolac type epoxy resin, "Epiclon N-775" manufactured by Dainippon Ink and Chemicals, Inc. Epoxy Co., Ltd. "Epicoat 152" and "Epicoat 154", Dow
"DEN431" and "DEN438" manufactured by Chemical Co., "EPN1138" manufactured by Ciba Co., Ltd., and the like, and triglycidyl isocyanurate include "TEPIC-G" manufactured by Nissan Chemical Industries, Ltd.,
"TEPIC-S" and "TEPIC-P" and the like are bisphenol diglycidyl ether as "Epicoat 828", "Epicoat 1001" manufactured by Yuka Shell Epoxy Co., Ltd.,
Examples include, but are not limited to, "Epicoat 1004", "Epicoat 1007", "Epicoat 1009", and the like.

(E) When one or more selected from latent heat curing agents, heat curing agents that are solid at room temperature, and heat curing accelerators are used, conventionally known agents such as "new epoxy resin" are used. (Published by Shokodo, May 1985), pages 164 to 263 and 356 to 405, "Crosslinking Agent Handbook" (published by Taisei Co., October 1981), pages 606 to 655 Among these, those having good storage stability are selected.
(E) can be used in the range of 0 to 10% by weight in the photo solder resist composition. As the latent thermosetting agent, boron trifluoride-amine complex, dicyandiamide (DICY) and its derivatives, organic acid hydrazide,
Diaminomaleonitrile (DAMN) and its derivatives, melamine and its derivatives, guanamine and its derivatives, amine imide
(AI), polyamine salts, etc.

As the thermosetting agent which is solid at room temperature, metaphenylenediamine (MP-DA), diaminodiphenylmethane (D
DM), diaminodiphenyl sulfone (DDS), aromatic amines such as "Hardener HT972" manufactured by Ciba-Geigy, phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimer) Melitate), aromatic acid anhydrides such as 3,3 ′, 4,4′-benzophenone tetracarboxylic acid anhydride, maleic anhydride, succinic anhydride, and cyclic aliphatic acid anhydrides such as tetrahydrophthalic anhydride. is there. Examples of thermosetting accelerators are metal salts of acetylacetone such as acetylacetonate Zn and acetylacetonate Cr, enamine, tin octylate, quaternary phosphonium salts, triphenylphosphine, 1,8-diazabicyclo (5,4,0) Undecene-7 and its 2-ethylhexanoate and phenol salts, imidazole, imidazolium salts, triethanolamine borate and the like can be mentioned.

The (F) ethylenically unsaturated compound having no epoxy group is used in the range where the workability is not deteriorated in order to further improve the physical properties, that is, in the range of 0 to 50% by weight in the photo solder resist composition. be able to. Such ethylenically unsaturated compounds include ethyl (meth)
Acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, α-alkylstyrene, oligoester (meth) monoacrylate, (meth) acrylic acid and the like (meth ) Acrylates, ethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, neopentyl glycol (meth) acrylate, tetramethylolmethane di (meth)
Acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2-hydroxy-1- (meth) acryloxy-3- (Meta)
Acrylate, urethane (meth) acrylate, diallyl phthalates and the like, and mixtures thereof can be used.

(G) One or more selected from organic solvents and water dissolve or disperse each component of the photo solder resist composition of the present invention, and for the purpose of adjusting the viscosity, the photo solder resist composition. It is used in the range of 0 to 70% by weight. (G) is appropriately selected in consideration of solubility, dispersibility, boiling point, influence on human body, etc. of each component.

(H) Other additives may be used, if necessary, in a range that does not impair the performance of the photosolder resist composition of the present invention, that is, in a range of 0 to 60% by weight in the photosolder resist composition. it can. Other additives include dyes and pigments for making it easier to confirm the coating state,
Thixotropic agent for adjusting fluidity, extender pigment for adjusting viscosity and facilitating development, polymerization inhibitor for preventing dark reaction and improving storage stability, adhesion improver, antioxidant. , Defoaming agents, thermal polymerization initiators, etc., but not limited to these. Examples of dyes and pigments include phthalocyanine green and titanium white, and examples of thixotropic agents include finely divided silica. Examples of extender pigments include silica, talc, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, precipitated barium carbonate, barium titanate and the like.
Examples of the polymerization inhibitor include hydroquinone and phenothiazine, and examples of the defoaming agent include silicone type, hydrocarbon type, acrylic type and the like.

The above (A) and, if necessary, (B)-
(H) is mixed and, if necessary, kneaded or mixed by a kneading means such as a triple roll, a ball mill, a sand mill or a stirring means such as a super mixer or a planetary mixer to obtain the photo solder resist composition of the present invention. To be The obtained photo solder resist composition,
Generally 5 to 10 on a printed wiring board with a copper circuit
It is applied with a coating thickness of 0 μm. As the coating means, the entire surface printing by the screen printing method is generally used at present, but any coating means including this can be used as long as it can be coated uniformly. For example, a spray coater, a hot melt coater, a bar coater, an applicator, a blade coater, a knife coater, an air knife coater, a curtain flow coater, a roll coater, a gravure coater, an offset printing, a dip coating, a brush coating, and any other conventional method can be used.

After coating, if necessary, prebaking, that is, temporary drying is performed in a hot-air oven or a far-infrared oven to make the surface tack-free. The prebaking temperature is preferably about 50 to 100 ° C. Next, exposure with active energy rays is performed using a negative mask in which only the portions to be solder-plated do not pass active energy rays. As the negative mask, a negative film is used when the active energy rays are ultraviolet rays, a metallic mask is used when the active energy rays are ultraviolet rays, and a lead mask is used when the active energy rays are X-rays, but a simple negative film can be used. Therefore, ultraviolet rays are often used as active energy rays in the production of printed wiring boards. The irradiation dose of ultraviolet rays is about 10 to 1000 mJ / cm ² .

After the exposure, a weak alkaline solution such as a dilute aqueous solution of sodium carbonate is used as a developing solution and development is carried out by means of spraying, dipping or the like, and the unexposed portion is removed by the action of dissolution, swelling or peeling. Next, post-curing is performed by heating in a hot-air oven, a far-infrared oven, or the like or UV irradiation. The photo solder resist is applied through the above steps.

[0026]

EXAMPLES Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the scope of rights of the present invention. In the examples, "part" means "part by weight" and "%" means "% by weight".

[Synthesis Example 1] Methyl methacrylate 110.3 g
(66.7 mol%), acrylic acid 39.7 g (33.3 mol%) in 205 g of cellosolve acetate reacted in a nitrogen stream with 3.0 g of benzoyl peroxide as a polymerization initiator, solid content 41.5%, active energy of weight average molecular weight 37,000 A linear curable resin precursor was obtained. After sufficiently cooling, attach a trap, hydroquinone 0.24g as polymerization inhibitor, boron trifluoride diethyl ether complex 0.4g as catalyst, hexane as azeotropic solvent.
20 g of toluene, 10 g of toluene, and 0.5 equivalent of hydroxyethyl methacrylate (44.1 g) as a radically polymerizable monohydric alcohol with respect to the acrylic acid moiety were added, and a condensation reaction was carried out at 150 ° C. for 8 hours. Dry air was continuously blown in during the reaction. An active energy ray-curable resin (a1) having a solid content of 41.1% and an acid value of 149 mgKOH / g was obtained.

[Synthesis Example 2] Methyl methacrylate 110.3 g
(66.7 mol%), acrylic acid 39.7 g (33.3 mol%) in 205 g of cellosolve acetate was reacted under a nitrogen stream with 6.0 g of benzoyl peroxide as a polymerization initiator, solid content 41.5%, active energy of weight average molecular weight 15,000. A linear curable resin precursor was obtained. After sufficiently cooling, a trap was attached, and hydroquinone (0.24 g) as a polymerization inhibitor, acetylacetone iron (III) 0.4 g as a catalyst, hexane 20 g and toluene 10 g as an azeotropic solvent, and a radical-polymerizable monohydric alcohol as an acrylic acid moiety 0.5 Equivalent amount of hydroxyethyl methacrylate (44.1 g) was added, and the condensation reaction was carried out at 150 ° C. for 8 hours. Dry air was continuously blown in during the reaction. Solid content 4
4.2% active energy ray curable resin with acid value 156mgKOH / g
(a2) was obtained.

[Synthesis Example 3] Styrene / maleic anhydride copolymer ("Admast 1000" manufactured by Idemitsu Petrochemical Co., Ltd., average molecular weight 6,500, maleic anhydride content 50 mol%) 369.
9g, cellosolve acetate 226.6g, triethylamine 4.
2 g, hydroquinone 0.7 g was charged into a flask, the temperature was raised to 90 ° C., 0.55 equivalents of 2-hydroxyethyl acrylate (108.4 g) with respect to the maleic anhydride residue was added dropwise over 30 minutes,
Then, the mixture was reacted for 6 hours. Bubbling was continued during the reaction. An active energy ray-curable resin (R) having a solid content of 54.0% and an acid value of 110 mgKOH / g was obtained.

Example 1 A photo solder resist composition having the following formulation was prepared. (A), (C), (E), (H1), (H
2) and (H3) were premixed and then thoroughly kneaded with a three-roll mill. (D) is dissolved in (G) in advance, and (F), (H
The kneaded product was mixed with 4) in a small planetary mixer. (A) Active energy ray curable resin (a1) 500 parts (C) Photopolymerization initiator 2,4-diethylthioxanthone 52 parts (D) Epoxy compound Cresol novolac type epoxy 120 parts (Dainippon Ink and Chemicals, Inc.) "Epiclone N-695") (E) Latent heat curing agent dicyandiamide 5 parts (F) Ethylenically unsaturated compound trimethylolpropane triacrylate ("NK Ester A-TMPT" manufactured by Shin Nakamura Chemical Co., Ltd.) 155 parts (G ) Solvent Cellosolve acetate 100 parts (H1) Coloring material Copper phthalocyanine green 5 parts (Toyo Ink Mfg. Co., Ltd. "Rionol Green 2YS") (H2) Thixotropic agent Fine silica 40 parts (Nippon Silica Industry Co., Ltd. "Nipseal" N-300A ”) (H3) Body pigment Talc (manufactured by Fuji Talc Co., Ltd.) 120 parts (H4) Defoamer Silicone 16 Department (Toray Dow Corning Silicone Co., Ltd.)

The photosolder resist composition thus obtained was evaluated by the following test methods using the following three types of test bodies. The results are shown in Table 1. The conditions of each step were as follows, unless otherwise specified. Specimen 1: Copper-clad laminate (FR-4) Specimen 2: Printed wiring board for testing (FR-4, minimum circuit width
0.1mm (4 between pins) Specimen 3: IPC test pattern (FR-4)

Coating: Screen printing method, whole surface coating using 150 mesh Tetron plate Pre-bake: Circulating hot air oven, 75 ° C / 30 minutes Exposure: "HMW680GW" manufactured by Oak Co., Ltd. (using 2 7kw metal halide lamps) Exposure intensity 35 mW / cm ² (at wavelength 365 nm) Exposure amount 300 mJ / cm ² Development: 1% sodium carbonate solution, liquid temperature 30 ° C, spray pressure 3 kg / cm ² , time 60 seconds, shower water washing 30 seconds Post cure: circulation type Use hot stove, 140 ℃ / 40 minutes

○ Pot life test The photo solder resist composition which had been left for 24, 48, 72, 96 and 120 hours after the preparation was applied to the test body 1 and prebaked. The developability was evaluated when the development was performed 10 minutes after the prebaking. The evaluation criteria were as follows. ○ ---- Fully developed □ ---- Slight development residue (to the extent that no green color remains) △ ---- Clear development residue (green color remains) ×- --Almost not developed

○ Leavable time test after pre-baking Test body 1 was coated and pre-baked for 24, 48, 72, 9
Specimens that were left for 6 and 120 hours were prepared and the developability was evaluated. The evaluation criteria were the same as in the pot life test. ○ Adhesion test A test body was prepared by subjecting the test body 1 to coating, prebaking and exposure. The exposure was performed so that the entire surface was irradiated with ultraviolet light. Ten
After leaving for a minute, cross-cutting was performed according to JIS D-0202, and then cellophane tape peeling was performed, and the number of remaining portions without peeling off the film was counted.

Water Resistance Flux Test Using the test body 2, a test body was prepared through all steps from coating to post cure. A highly active water-soluble flux (“K-183” manufactured by Alpha Metals Co., Ltd.) was applied to the entire surface, left standing vertically for 3 minutes to remove excess flux, and then preheated at 130 ° C. for 1 minute, 260 It was immersed in a molten solder bath at ℃ for 20 seconds. After leaving it to cool for 1 minute, it was washed with water and the water droplets were wiped off cleanly. After the treatment, the appearance was observed and the cellophane peeling was performed at the position of the minimum circuit width. The evaluation criteria are shown below. 5 ---- No whitening on appearance, no peeling with cellophane peeling 4 ---- No whitening on appearance, part of small-diameter through-hole peeling off with cellophane peeling 3 ---- Small whitening on appearance , Scotch tape peel with peeling at fine lines or edges (20% or less) 2 ---- Large whitening on appearance, peeling with Sellotape peel at fine lines or edges (20% or more) 1 ---- Appearance Large whitening on top, overall peeling of thin and thick lines

Example 2 (D) Same as Example 1 except that the epoxy compound “Epiclone N-695” was replaced with bisphenol A type epoxy (“Epicote 1007” manufactured by Yuka Shell Epoxy Co., Ltd.). Then, a photo solder resist composition was prepared and evaluated. Example 3 A photosolder resist composition was prepared and evaluated in the same manner as in Example 1 except that (A) the active energy ray-curable resin (a1) was replaced with (a2).

Example 4 (B) Example except that 7 parts of a silane coupling agent (γ-mercaptopropyltrimethoxysilane, “SH-6062” manufactured by Toray Dow Corning Silicone Co., Ltd.) was added. 1
A photo solder resist composition was prepared and evaluated in the same manner as in. Comparative Example A photosolder resist composition was prepared and evaluated in the same manner as in Example 1 except that (A) the active energy ray-curable resin (a1) was replaced with (R).

[0038]

[Table 1]

[0039]

EFFECTS OF THE INVENTION According to the present invention, it has excellent properties such as chemical resistance, solvent resistance, water resistance, moisture resistance, alkali resistance, and water-soluble flux resistance. A photosolder resist composition having a significantly improved post-leaving time was obtained, and the workability of the photosolder resist was improved.

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[Procedure amendment]

[Submission date] December 17, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

As the polymerizable monohydric alcohol, hydroxyalkyl (meth) acrylate, allyl alcohol,
Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polycaprolactone mono (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, neopentyl glycol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, tetramethylolmethane tri (meth) acrylate, di (2- (meth) acryloyloxyethyl) acid phosphate, glycerol di (meth) acrylate, and their (meth) acryloyl Examples include, but are not limited to, those having an ethylene oxide group, a propylene oxide group, a caproic acid group or the like between a group and a hydroxyl group, or a phosphoric acid group and a (meth) acryloyloxyethyl group. It is not.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display H05K 3/28 D

Claims (4)

[Claims] 1. A photo solder resist composition comprising a partially esterified product of a polymer of an unsaturated monocarboxylic acid or a copolymer with another ethylenically unsaturated compound by a radically polymerizable monohydric alcohol. 2. The photo solder resist composition according to claim 1, further comprising a silane coupling agent. 3. A silane coupling agent has at least one functional group selected from an alkoxysilyl group, a chlorosilyl group and an aminosilyl group as a first functional group, and a vinyl group, an amino group and a mercapto as a second functional group. The photosolder resist composition according to claim 2, which has one or more kinds of functional groups selected from a group, an epoxy group, and a (meth) acryloyl group. 4. The photo solder resist composition according to claim 3, wherein the second functional group of the silane coupling agent is a mercapto group or an epoxy group.