JPH0952925A - Photopolymerizable resin composition and cured material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition comprising a specific urethane modified vinyl ester resin and a photopolymerization initiator, having adhesivity to a substrate, pressure cooker resistance, heat resistance and nontack and developing properties, suitable as a solder-resist. SOLUTION: A vinyl ester resin obtained by reacting (A) an epoxy compound containing one or more epoxy groups (preferably a bisphenol type epoxy resin, etc.) with (B) an unsaturated-basic acid (preferably acrylic acid) or a mixture of the resin with (C) a carboxylcontaining diol compound (preferably dimethylolbutanoic acid, etc.) is reacted with (D) a polyisocyanate component containing >=1.5 isocyanate groups (preferably isophorone diisocyanate) to give a urethane-modified vinyl ester resin. Further this resin or a urethane-modified acid addition vinyl ester resin obtained by reacting the resin with (E) a polybasic acid anhydride (preferably tetrahydrophthalic acid anhydride) is mixed with (F) a photopolymerizationinitiator.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerizable resin composition, particularly a solder resist resin composition and a cured product thereof. The photopolymerizable resin composition of the present invention has high adhesion to a substrate, pressure cooker resistance and the like, and since the composition has non-adhesiveness (tack-free property) and developability. A wide range of applications are possible.

[0002]

2. Description of the Related Art Heretofore, an epoxy resin type thermosetting solder resist composition has been used as a solder resist composition.
From the viewpoint of energy saving and workability, there has been a shift to the use of a UV-curable solder resist composition capable of developing a diluted alkali. Such a dilute alkali developable UV-curable solder resist composition is patterned by a photographic method, but since it is superior in fineness as compared with the screen printing method, its application to electric and electronic parts is widened, For example, there is a strong demand for an additive method using electroless copper plating for forming fine wiring or a ball grid array method for sealing IC chips.

[0003]

However, the current dilute alkali-developable UV-curable solder resist composition, for example, a novolac type epoxy resin described in Japanese Patent Publication No. 1-54390 and a reaction product of acrylic acid, and a polybase. A cured product of a solder resist composition mainly composed of a reaction product of an acid anhydride has excellent heat resistance, but on the other hand, the cured product is too hard and a peeling phenomenon occurs between the coating film and the substrate during thermal history. However, there is a problem that the copper foil on the substrate is corroded. or,
In order to prevent such a peeling phenomenon between the coating film and the substrate during heat history, an attempt to use a flexible alkali-developable urethane (meth) acrylate is disclosed, for example, in JP-A-6-206956. As shown, (a) a compound (c) which is a reaction product of a trifunctional or higher functional polyol compound and a polybasic acid anhydride (b) and has at least one carboxyl group and at least two hydroxyl groups in the molecule. Organic polyisocyanate (d) Hydroxyl group-containing (meth) acrylate (e)
Although a method using a reaction product with is also known, in this method, since double bonds can be introduced only at both ends in one molecule, the double bond equivalent becomes large, and the crosslinking density becomes small, There was a drawback that the heat resistance of the cured product was poor.
Under these circumstances, the present invention aims to provide a photopolymerizable resin composition suitable as a resist film, especially a solder resist, which can be used under high temperature and high humidity conditions while maintaining good heat resistance. It is a thing.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that a vinyl ester resin or a mixture of the vinyl ester resin and a diol compound having a carboxyl group is treated with a polyisocyanate component. By developing a photopolymerizable resin composition that can be developed by chain extension, it is found that the cured film has pressure cooker resistance, solder heat resistance, electroless gold plating resistance, etc., and the resin composition is a resist. The present invention has been completed by finding that it is suitable as an ink, especially as a solder resist. That is, the present invention
(1) Urethane-modified vinyl ester resin (A), or urethane-modified acid-added vinyl ester resin (A ') obtained by adding polybasic acid anhydride (B) to (A) and photopolymerization initiator (C) Wherein the (A) is 1.
Vinyl ester resin (F) or (F) obtained by reacting an epoxy compound (D) having two or more epoxy groups with an unsaturated monobasic acid (E) and at least 1 in one molecule.
A photopolymerizable resin obtained by reacting a mixture with a diol compound (G) having one carboxyl group with a polyisocyanate component (H) having an average of 1.5 or more isocyanates in one molecule. The composition, (2) the photopolymerizable resin composition according to the above (1), which further comprises a polymerizable reactive diluent (I), and (3) the epoxy compound (D) has an average of 1 in one molecule. The acid value of the photopolymerizable resin composition according to (1) or (2), which has two to four epoxy groups, and (4) the urethane-modified vinyl ester resin (A), is 40 to 130. The photopolymerizable resin composition according to the above (1) or (2), wherein (5) (A) is a polyisocyanate component (H) with respect to a hydroxyl group in (F) or a mixture of (F) and (G). Isocyanate group equivalent ratio is 0.3- 2.0 is obtained by reacting in (1) or (2) a photopolymerizable resin composition. (6) Bisphenol type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin and alicyclic epoxy resin having a nucleus number of 1 in which (D) has 1.5 to 2.5 epoxy groups in one molecule. The photopolymerizable resin composition according to (1) or (2), which is at least one selected from the group consisting of resins, (7) the polyisocyanate component (H) is isophorone diisocyanate (IPDI), xylylene diisocyanate ( XD
I), hydrogenated xylylene diisocyanate (H6XD
I), tetramethylxylylene diisocyanate (TM)
XDI), which is at least one selected from the group consisting of (1) or (2),
(8) The above (1), (2), (3), (4), (5), (6) in which the photopolymerizable resin is a solder resist resin composition.
Alternatively, the photopolymerizable resin composition according to (7), or (9) a cured product obtained by curing the photopolymerizable resin composition according to (1) or (8).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The urethane-modified vinyl ester resin (A) used in the present invention comprises an epoxy compound (D) having an average of 1.2 or more epoxy groups in one molecule and an unsaturated monobasic acid (E). And a mixture of a vinyl ester resin (F) or (F) obtained by reacting with a diol compound (G) having at least one carboxyl group in one molecule, and an average of 1.5 in one molecule. It can be obtained by reacting with a polyisocyanate component (H) having one or more isocyanates. Epoxy compound (A)
Is required to contain 1.2 or more epoxy groups on average in one molecule, preferably 1.5 to 2.5, more preferably 1.8 to 2.2. Can be used for
Examples of such epoxy resin include bisphenol type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, alicyclic epoxy resin and the like. As an example of the bisphenol type epoxy resin, Epotote YD1 manufactured by Tohto Kasei Co., Ltd.
28, YD011, YD014, YD017, YD90
1, YD904, Epicoat 828, 1001, 1004, 1007, 100 manufactured by Yuka Shell Epoxy Co., Ltd.
9. Sumitomo Chemical Co., Ltd. Sumiepoxy ELA128, E
Bisphenol A type epoxy resin represented by SA011, ESA014, ESA017, Epotote YDF170, YDF2001 manufactured by Tohto Kasei Co., Ltd., Bisphenol F type epoxy resin represented by Epicoat 807 manufactured by Yuka Shell Epoxy Co., Ltd., Japaneseized EB manufactured by Yakuhin Co., Ltd.
Bisphenol S type epoxy resin represented by PS-300, Epotote YDB400, Y manufactured by Tohto Kasei Co., Ltd.
DB406, YDB412, Yuka Shell Epoxy Co., Ltd.
Examples thereof include Epicoat 5050 and 5051 manufactured by Sumitomo Chemical Co., Ltd., and brominated epoxy resins represented by Sumiepoxy ELB240 and ELB250 manufactured by Sumitomo Chemical Co., Ltd.

An example of the glycidyl ether type epoxy resin is Denacol EX-810 manufactured by Nagase Kasei Co., Ltd.
Ethylene glycol diglycidyl ether represented by, and propylene glycol diglycidyl ether represented by Denacol EX-911 manufactured by Nagase Kasei Co., Ltd.
Hydroquinone diglycidyl ether represented by Denacol EX-203 manufactured by Nagase Kasei Co., Ltd.
Examples thereof include cyclohexanedimethanol diglycidyl ether typified by Hero Japan MK-107 manufactured by i Japan Co., Ltd. Examples of the glycidyl ester type epoxy resin include adipic acid glycidyl ester represented by Denacol EX-701 manufactured by Nagase Kasei Co., Ltd. and orthophthalic acid diglycidyl ester represented by Denacol EX-721 manufactured by Nagase Kasei Co., Ltd. , Diglycidyl terephthalate represented by Denacol EX-711 manufactured by Nagase Kasei Co., Ltd., Sakamoto Yakuhin Co., Ltd.
Hexahydrophthalic acid diglycidyl ester typified by HHPA manufactured by K.K. Examples of the alicyclic epoxy resin include Celoxide 2021 and Celoxide 3000 manufactured by Daicel Chemical Industries, Ltd. These can be used alone or in combination of two or more. The epoxy resin used in the present invention is preferably a bisphenol type epoxy resin having a small number of hydroxyl groups in the resin, a bisphenol type epoxy resin, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, or an alicyclic epoxy resin. Next, examples of unsaturated monobasic acid (E) include acrylic acid, methacrylic acid, crotonic acid,
Examples thereof include cinnamic acid and a reaction product of a dibasic acid anhydride with an alcohol having at least one unsaturated group in one molecule. Examples of the dibasic acid anhydride used in the above reaction product include maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Examples of the alcohol having an unsaturated group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate and the like. It is particularly preferable to use acrylic acid.

In the reaction of the epoxy compound (D) with the unsaturated monobasic acid (E), the equivalent ratio of the unsaturated monobasic acid (E) to the epoxy group of the epoxy compound (D) is 0.8 to 1.
It is preferable that the reaction is carried out to be 2, and it is particularly preferably about 0.9 to 1.1. During the reaction, it is effective to use a reaction catalyst, and for example, a tertiary amine, a quaternary ammonium salt, phosphines, antimony, an organometallic salt or the like can be used. Examples of tertiary amines include triethylamine, pyridine, dimethylbenzylamine and the like. Examples of the quaternary ammonium salt include triethylbenzylammonium chloride, triethylbenzylammonium bromide, tetramethylammonium iodide and the like. Examples of phosphines include tributylphosphine and triphenylphosphine.
Examples of antimonies include triphenyl antimony and the like. Examples of organic metal salts include lithium naphthenate, chromium acetate, chromium octylate, chromium naphthenate, iron naphthenate and the like.
The catalyst is a vinyl ester resin (F) 1 which is a reaction product.
It can be added in a proportion of 0.001 to 5 parts by weight with respect to 00 parts by weight.

Further, it is desirable to blow air or use a polymerization inhibitor for the purpose of preventing gelation during the reaction.
Examples of the polymerization inhibitor include hydroquinone, p-toluquinone, p-methoxyphenol, phenothiazine, triphenylantimony, copper chloride and the like. The polymerization inhibitor is a vinyl ester resin (F) 10 which is a reaction product.
It can be added in a proportion of 0.001 to 2 parts by weight with respect to 0 parts by weight. Furthermore, in order to enhance the stirring efficiency during the reaction, it is effective to add a diluent in advance during the reaction.
Examples of diluents include methyl ethyl ketone, toluene,
Propylene glycol monomethyl ether acetate,
Carbitol acetate, other petroleum solvent (eg, Ipsol, manufactured by Idemitsu Petrochemical Co., Ltd., boiling point 184.5-2)
07.5 ° C.) and the like. In addition to the above diluents, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate. Acrylate, pentaerythritol diacrylate monostearate [Anilotx M-233 manufactured by Toagosei Kagaku KK], fatty acid-modified dipentaerythritol polyacrylate (Aronix M-430 manufactured by Toagosei Kagaku KK), polyester acrylate, and dibasic A polymerizable reactive compound typified by a reaction product of an acid anhydride and an alcohol having at least one unsaturated group in one molecule can be shared as a diluent. The reaction temperature can be synthesized at 50 to 160 ° C, preferably 80 to 120 ° C. Next, a mixture of the vinyl ester resin (F) or (F) and a diol compound (G) having at least one carboxyl group in one molecule, and a poly having an average of 1.5 or more isocyanates in one molecule. Isocyanate component (H)
Are made to react.

Examples of the diol compound (G) having at least one carboxyl group in one molecule include dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolvaleric acid and dimethylolcaproic acid. Can be mentioned. Especially,
It is preferable to use dimethylolpropionic acid or dimethylolbutanoic acid. Further, the ratio of the diol compound (G) to the vinyl ester resin (F) is preferably 1.0 or less, particularly preferably 0.6 or less in terms of an equivalent ratio. Diol compound (G)
When the ratio of the vinyl ester resin to the vinyl ester resin (F) is greater than 1.0, the double bond equivalent is large, the crosslink density is small, and the cured coating film has poor solder heat resistance and electroless gold plating resistance. It may get worse. Examples of the polyisocyanate component (H) include isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H6XDI), tetramethylxylylene diisocyanate (TMXDI), and paraphenylene. Diisocyanate (PPDI), Tolylene diisocyanate (TD
I), tolidine isocyanate (TODI), 4, 4 '
-Diphenylmethane diisocyanate (MDI), naphthylene diisocyanate (NDI), lysine isocyanate (LDI), hexamethylene diisocyanate (H
DI), cyclohexyl diisocyanate (CHP
I), dicyclohexylmethane diisocyanate (HM
DI), isopropylidene bis (4-cyclohexyl isocyanate) (IPC) and the like. From the viewpoint of developability and tack-free property, isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H6X
DI), tetramethylxylylene diisocyanate (T
The use of MXDI) is preferred. In addition, allophanates, biurets, trimers and the like of these polyisocyanate compounds can also be mentioned as preferred examples.
Further, a monoisocyanate compound such as phenyl isocyanate, isocyanate ethyl methacrylate, m-isopropenyl-α, α'-dimethylbenzoyl isocyanate can also be used as a mixture with the above polyisocyanate.

Urethane-modified by reacting a vinyl ester resin (F) or a mixture of (F) and a diol compound (G) with a polyisocyanate component (H) having an average of 1.5 or more isocyanates in one molecule. In the reaction for obtaining the vinyl ester resin (A), the equivalent ratio of the isocyanate group of the diisocyanate (H) to the hydroxyl group of the vinyl ester resin (F) and the diol compound (G) is set to 0.3 to 1.0. It is preferable that the reaction is carried out in the following manner, but it is more preferably 0.4 to 0.8. When the charging equivalent ratio is less than 0.3, the non-adhesiveness (tack-free property) of the solder resist resin composition may not necessarily be good because the molecular weight does not increase so much, and the charging equivalent ratio is 1 If it is larger than 0.0, the developability may be deteriorated. It is effective to use a reaction catalyst during the reaction, and for example, a tertiary amine, an organometallic compound or the like can be used. Examples of tertiary amines include triethylamine, N, N-dimethylcyclohexylamine, triethylenediamine and the like. Examples of organometallic compounds include stannas octoate, dibutyltin diacetate, dibutyltin dilaurate, and the like. The catalyst can be added in a proportion of 0.001 to 5 parts by weight with respect to 100 parts by weight of the urethane-modified vinyl ester (A) which is a reaction product. The reaction temperature can be synthesized at 30 to 130 ° C, preferably 50 to 120 ° C. The urethane-modified vinyl ester resin (A) thus obtained may be blended with the photopolymerization initiator (C) as it is, but some or all of the hydroxyl groups present in (A) are polybasic. Acid anhydride (B)
The urethane modified acid-added vinyl ester resin (A ') may be mixed with (C). Examples of the polybasic acid anhydride (B) to be reacted with the urethane-modified vinyl ester (A) include maleic anhydride, succinic anhydride,
Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 1,3,3a, 4,5,9b-hexahydro-
(Tetrahydro-2,5-dioxo-3-furanyl)-
Naphtho [1,2-C] furan-1,3-dione (TDA-100 manufactured by Shin Nippon Rika Co., Ltd.), 5- (tetrahydro-2,5-dioxo-3-furanyl) -3-methyl-3
-Cyclohexene-1,2-dicarboxylic acid anhydride (Epiclone B-4400 manufactured by Dainippon Ink and Chemicals, Inc.) and the like can be mentioned. It is particularly preferable to use tetrahydrophthalic anhydride or hexahydrophthalic anhydride.

The reaction of the urethane-modified vinyl ester resin (A) with the polybasic acid anhydride (B) is carried out so that the equivalent ratio of the polybasic acid anhydride (B) to the hydroxyl group in (A) is 1 or less. Can be reacted. It is effective to use a reaction catalyst during the reaction. For example, when a tertiary amine, a quaternary ammonium salt or the like is used, the reaction time can be significantly shortened. Reaction temperature is 50-160 ℃
Can be synthesized at 80 to 120 ° C.
The reaction time of this reaction at 120 ° C. is usually 15 minutes to 8 hours. The acid value (mgKOH / g) of the urethane-modified vinyl ester resin (A) or urethane-modified acid-added vinyl ester resin (A ′) thus obtained is 0 to 130.
However, it is preferably 20 to 130. The amount of (A) or (A ') contained in the photopolymerizable resin composition of the present invention is preferably 10 to 80% by weight, and particularly preferably 15 to 75% by weight in the photopolymerizable resin composition. Next, as the photopolymerization initiator (C), acetophenone-based, benzoin-based, benzophenone-based, thioxaton-based, phosphorus-based, or the like can be used. Examples of acetophenone type compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1.
-Phenylpropan-1-one, benzyl dimethyl ketal [Ciba Geigy Co., Ltd. Irgacure 65
1] 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one [Ciba-Geigy Co., Ltd. Irgacure 907] 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone [Ciba-Geigy Co., Ltd.] Irgacure 369] and the like. Examples of benzoin compounds include benzoin, benzoin methyl ether, and benzoin ethyl ether. Examples of the benzophenone series include benzophenone, hydroxybenzophenone, 4-phenylbenzophenone, 3, 3 ', 4, 4'
-Tetra (t-butylperoxycarbonyl) benzophenone [BTTB manufactured by NOF CORPORATION] and the like can be mentioned. Examples of thioxanthone-based compounds include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone [Nippon Kayaku Co., Ltd.].
Kayakyu DETX] and the like can be mentioned. Examples of phosphorus-based compounds include acylphosphine oxide [BA
SF manufactured by Lucitin TPO] and the like. In addition, a tertiary amine can be used in combination for promoting polymerization. Examples of tertiary amines include triethanolamine, ethyl 4-dimethylaminobenzoate, p, p'-
Examples thereof include tetramethyldiaminobenzophenone.

The amount of the photopolymerization initiator (C) contained in the photopolymerizable resin composition of the present invention is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight in the resin composition. The diluent (I) can be added to the photopolymerizable resin composition of the present invention during and / or after production. As the diluent, for example, acrylates and acrylamides can be used. Examples of acrylates include methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate, n-stearyl (Meth) acrylate, methoxy polyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) ac Rate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth)
Acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, pentaerythritol diacrylate monostearate [Aronix M-233 manufactured by Toagosei Kagaku KK], fatty acid-modified dipentaerythritol polyacrylate [Aronix M-430 manufactured by Toagosei Kagaku KK], polyester acrylate, And a reactive diluent such as a reaction product of a dibasic acid anhydride and an alcohol having at least one unsaturated group in one molecule. Examples of other diluents include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, methyl alcohol, ethyl alcohol, propyl alcohol, toluene, Examples thereof include solvents such as xylene and Ipsol of Idemitsu Petrochemical Co., Ltd.

The diluent (I) can be used alone or as a mixture of two or more kinds, and the amount thereof is preferably 2.5 to 80% by weight, particularly preferably 4% by weight based on the photopolymerizable resin composition. Is about 70% by weight. In the photopolymerizable resin composition of the present invention, various thermosetting or photocurable resins represented by epoxy resins, melamine resins, isocyanate resins and oxazoline resins can be mixed and used. Further, a curing agent for these resins may be used in combination.
These resins and curing agents can be used in an amount of 1 to 50% by weight based on the photopolymerizable resin composition. further,
A polymerization inhibitor, a filler, a defoaming agent, a coloring agent, a leveling agent, etc. can be added to the photopolymerizable resin composition of the present invention. Examples of the polymerization inhibitor include hydroquinone and p-
Toluquinone, phenothiazine, diketones and the like can be mentioned. Examples of the filler include talc, barium sulfate, silica and the like. Examples of the antifoaming agent include silicone oil. Examples of the coloring agent include phthalocyanine blue, leuco dye, carbon black, titanium oxide and the like. These additives are added to the photopolymerizable resin composition in an amount of 0.001-1
50% by weight is used.

The photopolymerizable resin composition of the present invention can be obtained by blending the blending components preferably in the above proportions and uniformly stirring and kneading with a resolver, a roll mill or the like. When the photopolymerizable resin composition of the present invention is used as a resist ink, it can be cured by the following method to obtain a cured product. That is, the photopolymerization of the present invention is applied to a printed wiring board by a method such as a screen printing method, a spray method, a curtain coating method, a roll coating method, a dip coating method, a doctor knife method or an electrostatic coating method in a film thickness of 10 to 200 μm. Of the organic resin composition, the coating film is dried at 60 to 110 ° C., and the organic solvent is removed. After drying, the negative film is brought into direct contact with the coating film, and is irradiated (exposed) with ultraviolet rays using a high pressure mercury lamp, a metal halide lamp or the like, and the unexposed portion is washed away with a dilute alkaline solution of about 1 to 2%,
Further, in order to improve various physical properties, irradiation with ultraviolet rays and / or heating (for example, at 100 to 200 ° C. for 30 to 60 minutes) causes sufficient curing to obtain a cured film.

[0015]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. All parts in the synthesis examples are parts by weight. Synthesis Example 1 Bisphenol A type epoxy resin [manufactured by Tohto Kasei Co., Ltd.,
YD128, epoxy equivalent 178] 688 parts (1.84
Mol), 265 parts of acrylic acid (3.68 mol), 0.1 part of hydroquinone, 596 parts of carbitol acetate and petroleum solvent (Ipsol 150, Idemitsu Petrochemical Co., Ltd.)
(Manufactured by Mitsui Chemicals Co., Ltd.), and heated to 100 ° C. and stirred to dissolve the reaction mixture. Then dimethylbenzylamine 1.
Charge 0 part, 110-120 ℃ while blowing air
After reacting for 6 hours, the acid value became 1 mgKOH / g. Next, the temperature in the system was lowered to 50 to 60 ° C., and 172 parts (1.16 mol) of dimethylolbutanoic acid, 446 parts (2 mol) of isophorone diisocyanate (IPDI) and 0.3 part of dibutyltin dilaurate were charged, 50-60 ° C
Was reacted for 6 hours, and it was confirmed by infrared absorption spectrum that the isocyanate was completely reacted. Next, 273.6 parts (1.8 mol) of tetrahydrophthalic anhydride was charged and allowed to react at 110 ° C. for 3 hours, and it was confirmed by infrared absorption spectrum that the acid anhydride was completely reacted. A photopolymerizable resin having a valency of 90 mgKOH / g and a nonvolatile content of 65% was obtained.

Synthesis Example 2 Bisphenol A type epoxy resin [manufactured by Tohto Kasei Co., Ltd.,
YD128, epoxy equivalent 178] 711 parts (1.9 mol), acrylic acid 273.6 parts (3.8 mol), hydroquinone 0.1 part, carbitol acetate 585 parts and petroleum solvent (ipsol 150, Idemitsu Petrochemical). (stock)
390 parts) were charged, heated to 100 ° C. and stirred to dissolve the reaction mixture. Then dimethylbenzylamine 1.
Charge 0 part, 110-120 ℃ while blowing air
After reacting for 6 hours, the acid value became 1 mgKOH / g. Next, the temperature in the system was lowered to 50 to 60 ° C., 162.8 parts (1.1 mol) of dimethylolbutanoic acid, 388 parts (2 mol) of hydrogenated xylylene diisocyanate (H6XDI), dibutyltin dilaurate of 0. Prepare 3 parts, 5
The reaction was carried out at 0 to 60 ° C. for 6 hours, and it was confirmed by infrared absorption spectrum that the isocyanate was completely reacted.
Then, 275 parts (1.81 mol) of tetrahydrophthalic anhydride was charged and reacted at 110 ° C. for 3 hours, and it was confirmed by infrared absorption spectrum that the acid anhydride was completely reacted, and the acid value of the nonvolatile component was 90 mgKOH. Nonvolatile content of 6 / g
5% of photopolymerizable resin was obtained.

Synthetic Example 3 552 parts (2.06 mol) of alicyclic epoxy resin [manufactured by Daicel Chemical Industries, Ltd., Celoxide 2021, epoxy equivalent 134], acrylic acid 296.6 parts (4.12)
Mol), 0.1 part of hydroquinone, 552 parts of carbitol acetate and 368 parts of petroleum-based solvent (Ipsol 150, manufactured by Idemitsu Petrochemical Co., Ltd.), and heated to 100 ° C. and stirred to dissolve the reaction mixture. Next, 1.0 part of dimethylbenzylamine was charged, and while blowing air, 1
When reacted at 10 to 120 ° C for 6 hours, the acid value is 1 mgK
It became OH / g. Then the temperature of the reaction mixture is raised to 50-6.
The temperature was lowered to 0 ° C, and 139 parts of dimethylolbutanoic acid (0.94
Mol), isophorone diisocyanate (IPDI) 44
6 parts (2 mol) and 0.3 part of dibutyltin dilaurate were charged and reacted at 50 to 60 ° C. for 6 hours, and it was confirmed by infrared absorption spectrum that isocyanate was completely reacted. 273.6 parts (1.8 mol) of tetrahydrophthalic anhydride was charged to the obtained reaction mixture and reacted at 110 ° C. for 3 hours, and it was confirmed by infrared absorption spectrum that the acid anhydride was completely reacted, Nonvolatile acid value is 90
A photopolymerizable resin having a nonvolatile content of 65% was obtained at mgKOH / g.

Synthesis Example 4 Alicyclic epoxy resin [manufactured by Daicel Chemical Industries, Ltd., Celoxide 2021, epoxy equivalent 134] 568 parts (2.12 mol), acrylic acid 305 parts (4.24 mol), hydroquinone 0. 1 part, 538 parts of carbitol acetate and 358 parts of petroleum-based solvent (Ipsol 150, manufactured by Idemitsu Petrochemical Co., Ltd.) were charged and heated to 100 ° C. and stirred to dissolve the reaction mixture. Next, 1.0 part of dimethylbenzylamine was charged, and while blowing air 11
When reacted at 0 to 120 ° C for 6 hours, the acid value is 1 mgKO
It became H / g. The temperature of the obtained reaction mixture is 50 to 6
The temperature was lowered to 0 ° C and 130 parts of dimethylolbutanoic acid (0.88
Mol), hydrogenated xylylene diisocyanate (H6XD
I) 388 parts (2 mol) and 0.3 part of dibutyltin dilaurate were charged and reacted at 50 to 60 ° C. for 6 hours, and it was confirmed by infrared absorption spectrum that isocyanate was completely reacted. Next, tetrahydrophthalic anhydride 2
72 parts (1.79 mol) were charged and reacted at 110 ° C. for 3 hours, and it was confirmed by infrared absorption spectrum that the acid anhydride was completely reacted, and the acid value of the nonvolatile component was 90 mgKO.
A photopolymerizable resin having a nonvolatile content of 65% at H / g was obtained. Synthesis Example 5 Cresol novolac type epoxy resin (Tohto Kasei Co., Ltd.)
YDCN701, epoxy equivalent 200) 200 parts (1 equivalent), acrylic acid 72 parts (1 mol), hydroquinone 0.1 part, carbitol acetate 117 parts and petroleum solvent (Ipsol 150, manufactured by Idemitsu Petrochemical Co., Ltd.) )
78 parts were charged, the mixture was heated to 100 ° C. and stirred to dissolve the reaction mixture. Next, 1.0 part of dimethylbenzylamine was charged, and the reaction was carried out at 110 to 120 ° C. for 6 hours while blowing air, so that the acid value became 1 mgKOH / g. Next, 88.2 parts (0.58 mol) of tetrahydrophthalic anhydride was charged and reacted at 110 ° C. for 3 hours to obtain a photopolymerizable resin having a solid content acid value of 90 mgKOH / g and a solid content of 65%. It was

Examples 1 to 4 and Comparative Example 1 A resist ink resin composition (main agent and curing agent) was prepared according to the following formulation. The photopolymerizable resins obtained in Synthesis Examples 1 to 4 were used in Examples 1 to 4, and the photopolymerizable resin obtained in Synthesis Example 5 was used in Comparative Example 1.

Table 1 Main agent Each photopolymerizable resin obtained in Synthesis Examples 1 to 154 parts by weight 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one (Irgacure 907, Ciba Geigy Corp.) 15 parts by weight 2,4-diethylthioxanthone (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.1 parts by weight carbitol acetate 8 parts by weight pentaerythritol diacrylate monostearate (Aronix M-233 Toa Gosei Chemical ( 12 parts by weight Other silica (with an average particle size of about 1 μ) 60 parts by weight Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.) 8 parts by weight Phthalocyanine green (coloring agent) 1.4 parts by weight Dicyandiamide (curing catalyst) 1.0 parts by weight Dimethyl silicone oil Silicon antifoaming agent (KF-69, manufactured by Shin-Etsu Silicone Co., Ltd.) 2.0 parts by weight Parts Talc 100 parts by weight Total 361.5 parts by weight

[0020]

[Table 2] Curing agent Carbitol acetate 10 parts by weight Petroleum solvent (Ipsol 150, manufactured by Idemitsu Petrochemical Co., Ltd.) 5 parts by weight Fatty acid-modified dipentaerythritol polyacrylate (Aronix M-430, manufactured by Toagosei Co., Ltd.) ) 10 parts by weight Others Bisphenol A type epoxy resin (YD901, manufactured by Tohto Kasei Co., Ltd.) 5 parts by weight Phenol novolac type epoxy resin (EPPN201, manufactured by Nippon Kayaku Co., Ltd.) 10 parts by weight triglycidyl ether isocyanurate (TEPIC) Nissan Chemical Co., Ltd.) 20 parts by weight Talc 10 parts by weight Barium sulfate 30 parts by weight Total 100 parts by weight The above-mentioned main agent and curing agent were separately kneaded by a resolver and then mixed to prepare. This was applied to a 1.6 mm thick printed circuit board by screen printing using a 180-mesh polyester screen plate so as to have a thickness of 25 μm, and the coating film was applied at 85 ° C. to 40 ° C.
It was dried for a minute and the solvent was removed. Then, the negative film having the resist pattern was deaerated and brought into close contact with the coating film. At this time, with respect to the resin composition before curing, the following evaluation was performed with respect to non-adhesiveness (dryness of coating film). The results are shown in [Table 3]. Non-Adhesiveness (Drying Property of Coating Film) The drying property of the coating film was evaluated according to JIS K-5400. ◯: No tack is observed at all Δ: Slight tack is observed x: Significant tack is observed. The amount of exposure of the adhered coating film by an ultraviolet irradiation device is 350
After irradiating with ultraviolet rays at mJ / cm ² , 1 at 30 ° C
% Sodium carbonate aqueous solution for 40 seconds, 2.0 kg / c
Development was carried out with a spray pressure of m ² to dissolve the unexposed portion. At this time, the following evaluations were performed on the developability of the unexposed area and the resolution of the pattern width. The results are shown in [Table 3].

Developability The developability was visually evaluated with a magnifying glass (150 times). ◯: During development, the unexposed portion was completely removed and development was possible. X: The unexposed portion is not removed even during development. Resolution Obtained from the pattern width of the solder resist film after development. After development, heat curing was carried out for 40 minutes with a hot air dryer at 150 ° C., and the following evaluations were made on the adhesion, pencil hardness, and pressure cooker resistance of the test piece having the cured film obtained. The results are shown in [Table 3]. 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 Pencil Hardness The hardness was measured under a load of 1 kg according to the test method of JIS K5400. Pressure cooker resistance A container (Taft Co., Ltd., Haft HAST TPC-4 manufactured by Tabai Co., Ltd.) in which a test piece was kept at 121 ° C., 2 atmospheric pressure and 100% relative humidity.
It was allowed to stand for 24 hours in 12-MD) and evaluated for changes in appearance and changes in copper foil. Change in appearance ◯: No floating, peeling, or whitening of the surface of the cured film. B: Part of the cured film floats, peels off, and surface whitening is observed. X: Floating, peeling and whitening of the surface are observed on the entire surface of the cured film. Change in copper foil ○: No discoloration is observed in the copper foil part. X: Discoloration is seen in the copper foil part.

[0021]

[Table 3] As is clear from the evaluation results in [Table 3], the resist ink resin composition of the present invention has good non-adhesiveness and developability, and its cured product has a high resolution, an excellent adhesion and a good pressure. Has cooker resistance.

[0022]

As described above, the photopolymerizable resin composition of the present invention has non-adhesiveness (tack-free property) and is exposed to ultraviolet rays selectively through a film having a pattern formed, In the formation of the solder resist pattern by developing the unexposed portion, the solder resist pattern can be developed, and the obtained cured product has resolution, adhesion and pressure cooker resistance. Further, the photopolymerizable resin composition of the present invention is inexpensive in comparison with a conventional cresol novolac type epoxy resin starting material, and has an advantage that the structure can be freely designed. Especially suitable as an ink for solder resist.

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

Claims (9)

[Claims] 1. A urethane-modified vinyl ester resin (A),
Alternatively, it comprises a urethane-modified acid-added vinyl ester resin (A ') obtained by adding a polybasic acid anhydride (B) to (A) and a photopolymerization initiator (C), and one molecule of the (A) is contained. A vinyl ester resin (F) or (F) obtained by reacting an epoxy compound (D) having 1.2 or more epoxy groups with an unsaturated monobasic acid (E) and at least 1 in one molecule A photopolymerizable resin obtained by reacting a mixture with a diol compound (G) having one carboxyl group with a polyisocyanate component (H) having an average of 1.5 or more isocyanates in one molecule. Composition. 2. The photopolymerizable resin composition according to claim 1, further comprising a diluent (I). 3. The epoxy compound (D) has an average of 1.2 to 4 epoxy groups in one molecule.
Alternatively, the photopolymerizable resin composition described in 2. 4. The photopolymerizable resin composition according to claim 1, wherein the urethane-modified vinyl ester resin (A) has an acid value of 20 to 130. 5. The equivalent ratio of the isocyanate groups of the polyisocyanate component (H) to the hydroxyl groups in (F) or the mixture of (F) and (G) is 0.3 to 1.0.
The photopolymerizable resin composition according to claim 1 or 2, which is obtained by reacting with. 6. A bisphenol type epoxy resin having a nucleus number of 1 having (D) 1.5 to 2.5 epoxy groups in one molecule, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin and an alicyclic ring. The photopolymerizable resin composition according to claim 1, which is at least one selected from the group consisting of formula epoxy resins. 7. The polyisocyanate component (H) is at least selected from the group consisting of isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H6XDI) and tetramethylxylylene diisocyanate (TMXDI). The photopolymerizable resin composition according to claim 1, which is one kind. 8. The photopolymerizable resin composition according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the photopolymerizable resin is a solder resist resin composition. 9. A cured product obtained by curing the photopolymerizable resin composition according to claim 1.