JPH0777800A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To provide a novel photosensitive resin composition excellent in heat resistance and chemical resistance and to provide a resist ink composition using the same having well-balanced properties. CONSTITUTION:This photosensitive resin composition contains the photosensitive resin A obtained by allowing (1) a compound having two or more of carboxylic anhydride group to react with (2) a compound having primary and/or secondary amine 0.1-1.0 equivalent to the carboxylic anhydride group and radical polymerizing group and (3) a compound having or no active hydrogen except primary or secondary amine 0.0-0.9 equivalent to the carboxylic anhydride group and the radical polymerizing group and a polymerization initiator B as essential components.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition based on a novel resin, and particularly in the field of electronic materials, a resist which is required to have heat resistance, chemical resistance and electrical insulation. The present invention relates to a composition useful as an ink or the like.

[0002]

2. Description of the Related Art Photosensitive resins cure rapidly and can be used for pattern formation by selective exposure, so that they have properties not found in thermosetting resins.
It is widely used in the fields of printing plate materials, adhesives, inks, resists, etc. In particular, it has come to be recognized as an important material in inks for solder resists for printed wiring boards. With the recent miniaturization of electronic devices, the density of components mounted on printed wiring boards is also increasing. Solder resist is used to prevent troubles when soldering components to the wiring board and to protect the circuit board after mounting the components for a long time. In order to deal with this, the screen printing type resist has been changed to a photo developing type resist. Further, from the viewpoint of improving the working environment and environmental protection, a method using an alkaline aqueous solution for the development has become the mainstream. In the solder resist, the alkali-soluble photosensitive resin, which is the main component of the solder resist, has an important influence on the performance.

As the photosensitive resin which has been used so far, the one which is described in JP-A-61-243869, which is obtained by reacting a novolac type epoxy resin with acrylic acid and further reacting with a dicarboxylic acid anhydride, is mainstream. Is. This resin is widely used because it has photosensitivity and alkali solubility and is said to exhibit good heat resistance due to its novolak type skeleton. However, as the manufacturing technology of printed circuit boards has advanced in recent years, higher performance has been required for solder resists.
Specifically, with the miniaturization of surface mount components, there is a need for a resist with higher resolution and higher insulation,
One of the reasons is that electroless plating technology has come to be frequently used in the production of wiring boards, and high chemical resistance is required. On the other hand, in order to improve the productivity in the production of printed wiring boards, it is necessary to shorten each process and improve the workability even in the work using the solder resist.
Many of these required performances are in a contradictory relationship, and if any one of them is improved, other properties will be impaired, so the formulation using this existing resin is already at its limit,
The development and introduction of new materials is essential for significant performance improvement.

Under these circumstances, many attempts have been made to develop a photosensitive resin, which is the main component of solder resist. Most of them use a new structure of epoxy resin, which replaces the novolac type epoxy resin as a raw material,
It is obtained by reacting acrylic acid and acid anhydride, and examples thereof include JP-A-2-173750 and JP-A-2-173750.
173751, JP-A-3-71137, JP-A-3-28
9656, JP-A-2-120308, JP-A-3-100
009 etc. are mentioned. Further, JP-A-3-172301 and JP-A-3-289655 are reported as those produced by reacting a part of a polymer having a carboxyl group with an epoxy compound having a photosensitive group. In addition, there is also reported that a resin having a photosensitive group and a carboxyl group is obtained by reacting a styrene-maleic anhydride copolymer resin with a radical-polymerizable alcohol, and examples thereof include JP-A-63- 205649, JP-A-2-23351, 2
-109052 is mentioned. Conventionally, many photosensitive resin compositions using these resins or solder resists using them are known, but workability during manufacturing of printed wiring boards, chemical resistance, and heat resistance during mounting are still known. , And subsequent long-term durability is not known to have sufficient performance.

[0005]

An object of the present invention is to provide a novel photosensitive resin composition having excellent heat resistance and chemical resistance, and a resist ink composition to which the photosensitive resin composition is applied and which has an excellent balance of properties. To provide things.

[0006]

[Means for Solving the Problems] In view of the above problems, the inventors have conducted earnest studies for the purpose of developing a novel photosensitive resin composition, and as a result, found the following composition and completed the invention. . That is, the present invention includes A) (1) a compound having two or more carboxylic acid anhydride groups, and (2) 0.1 to 1.0 equivalent of primary and / or 2 equivalents to the carboxylic acid anhydride groups.
A compound having a primary amine and a radical polymerizable group, and (3) having 0.0 to 0.9 equivalents of active hydrogen other than a primary or secondary amine and a radical polymerizable group with respect to the carboxylic acid anhydride group. Alternatively, it is characterized in that a photosensitive resin obtained by reacting with a compound that does not have it and B) a polymerization initiator are essential components. The radical polymerizable group of the resin in (A) is polymerized by the radical generated by the photopolymerization initiator of the component (B) to give a cured product. Further, the carboxylic acid anhydride group of the component (A) is converted into an amide group and a carboxyl group by the reaction with an amine, and when the carboxyl group causes adhesion to metals, solubility in alkalis, and addition of an epoxy compound, etc. Properties such as crosslinking reactivity with them are given to the resin.

The compound having two or more carboxylic acid anhydride groups used in the compound represented by (1) of the component A) in the present invention is not particularly limited, but a photosensitive resin is used as a resist ink. When it does, it reacts with the amine or active hydrogen compound shown in (2) to give a molecular weight of 600-
It is desirable to select one that falls within the range of 30,000. When the molecular weight is 600 or less, when it is actually used as a solder-resist ink, the drying property is poor when the solvent is removed after coating, which is not preferable. At 30,000 or more, when the photosensitive resin is alkali-developed and used,
This is not preferable because the developability is impaired.

Particularly preferably used as a compound having two or more carboxylic acid anhydride groups is maleic anhydride,
It is a copolymer of a polymerizable acid anhydride compound such as itaconic anhydride and another radically polymerizable monomer. As the polymerizable acid anhydride, maleic anhydride, which is industrially available at low cost, is preferable. The other radically polymerizable monomer is not particularly limited as long as it is a monomer that is copolymerizable with the above-mentioned polymerizable acid anhydride compound and does not react with the acid anhydride group under the conditions of the polymerization reaction. For example, olefinic hydrocarbons such as ethylene, propylene and butene, styrene monomers such as styrene, methylstyrene, chloromethylstyrene and vinylphenol, and methyl (meth) acrylate.
Acrylic monomers such as ethyl acetate, ethyl (meth) acrylate, butyl (meth) acrylate and acrylamide, vinyl ethers such as methyl vinyl ether and vinyl acetate or vinyl ester monomers are used. These may be used alone or in combination of two or more. Of these, aromatic monomers such as styrene impart heat resistance to the resin and are therefore particularly preferable when used as a resist ink.

As the compound having a primary and / or secondary amine and a polymerizing group (radical-polymerizable amine), allylamine, diallylamine, N-allyl-N-
N-allyl-N-alkylamines such as methylamine and allylaniline can be used. These may be used alone or in combination of two or more. Usually, industrially available allylamine or diallylamine is preferably used. When diallylamine is used, a cured product having excellent sensitivity and heat resistance can be obtained, and thus it is particularly preferable in applications where such performance is important.

A compound having or not having active hydrogen other than primary or secondary amine and a radical polymerizable group (radical polymerizable active hydrogen compound) is a compound capable of reacting with an acid anhydride group and at the time of reaction. Any compound that does not cause gelation may be used. Further, they may or may not have a radically polymerizable group. For example, methano-
Alcohols such as phenol, ethanol, (iso) propyl alcohol, methoxyethanol, carbitol, octyl alcohol, allyl alcohol, benzyl alcohol, lactic acid, phenol, cresol. -Phenols such as phenol, hydroxyethyl (meth) acrylate, N-methyl acrylamide, pentaerythritol triacryl-
It is also possible to use hydroxyl group-containing (meth) acrylates such as amides, acrylamides, amines such as methylamine, ethanolamine, butylamine, morpholine and amino acids, and inorganic compounds such as water and ammonia. These may be used alone or in combination of two or more.

The ratio of reacting the radically polymerizable amine and the radically polymerizable active hydrogen compound with a compound having two or more carboxylic acid anhydride groups is such that the radically polymerizable amine is 0.1 to 0.1% of the carboxylic acid anhydride groups. 1.0 equivalent and a radically polymerizable active hydrogen compound having a carboxylic acid anhydride group of 0.
It is preferably 0 to 0.9 equivalent. When the amount of the radically polymerizable amine is less than the above range, the characteristic feature of the present invention cannot be sufficiently exhibited. In particular, the sensitivity to light and the heat resistance of the cured product decrease. On the other hand, the radically polymerizable active hydrogen compound may be appropriately reacted with the remaining carboxylic acid anhydride group when the radically polymerizable amine is reacted in an amount of 0.1 to 1.0 equivalent of the carboxylic acid anhydride group. Properties of the photosensitive resin obtained by adding these, namely viscosity,
The solubility, heat resistance, photosensitivity, etc. can be adjusted. As long as the ratio of reacting the radically polymerizable amine and the radically polymerizable active hydrogen compound with the compound having two or more carboxylic acid anhydride groups satisfies the above range, leaving the acid anhydride group in the photosensitive resin. It doesn't have to be left. When the acid anhydride group remains, a crosslinking reaction can be carried out by adding an epoxy compound or the like to the composition using the acid anhydride group.

The reaction of the compound having two or more carboxylic acid anhydride groups with the radical-polymerizable amine and the radical-polymerizable active hydrogen compound is usually carried out in a suitable solvent or diluent. As the solvent and the diluent, those which do not gel the resin by reacting with an acid anhydride group or an amino group are used. The reaction is preferably performed in the range of 10 ° C to 200 ° C.

Next, as the photopolymerization initiator used in the present invention, benzoins such as benzoin, benzyl, benzoin methyl ether and benzoin isopropyl ether, benzoin alkyl ethers, acetophenone,
2,2-dimethoxy-2-phenylacetophenone,
2,2-diethoxy-2-phenylacetophenone,
1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4-
(Methylthio) phenyl "-2-morphono-propan-1-one, acetophenones such as N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-
Anthraquinones such as ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone and 2-aminoanthraquinone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,
Thioxanthones such as 4-diisopropylthioxanthone, acetophenone dimethyl ketal, ketals such as benzyl dimethyl ketal, benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone,
There are benzophenones such as 4,4′-bisdiethylaminobenzophenone and Michler's ketone and xanthones, which can be used alone or in combination of two or more kinds. Further, such a photopolymerization initiator is ethyl-4-
Dimethylaminobenzoate, 2- (dimethylamino)
Known conventional photosensitizers such as benzoic acid esters such as ethyl benzoate and tertiary amines such as triethylamine and triethanolamine can be used alone or in combination of two or more kinds.

The preferred range of the amount of the photopolymerization initiator used is 0.2 to 30 with respect to 100 parts by weight of the photosensitive resin (A).
Parts by weight, preferably 2 to 20 parts by weight. If it is less than this range, the sensitivity tends to be poor.

A diluent may be added to the photosensitive resin composition of the present invention in addition to the above essential components. Especially when the composition of the present invention is used as a resist ink, it is added as an essential component. As the diluent, a photopolymerizable vinyl type monomer and / or an organic solvent can be used.
Typical examples of the photopolymerizable vinyl-based monomer are 2
-Hydroxyethyl acrylate, hydroxyalkyl acrylate such as 2-hydroxybutyl acrylate, ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol
Glycol or other mono or diacrylate,
Acrylamides such as N, N-dimethyl acrylamide and N-methyl acrylamide, aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, trimethylolpropane, pentaerythritol and diether Polyphenols such as pentaerythritol or polyvalent acrylates of adducts of ethylene oxide, propylene oxide or ε-caprolactone, phenoxy acrylate, phenoxyethyl acrylate and the like -, Acrylates such as ethylene oxide or propylene oxide adducts thereof, epoxy acrylates derived from glycidyl ether such as trimethylolpropane triglycidyl ether, melamine acrylate And / or the above Les - methacrylates corresponding to the door - there is such as theft class. The sensitivity of the photosensitive resin composition of the present invention can be improved by adding these reactive diluents, especially polyfunctional acrylates.

Examples of the organic solvent include ketones such as methyl ethyl ketone, aromatic hydrocarbons such as toluene and tetramethylbenzene, glycol ethers such as methyl cellosolve, methyl carbitol and triethylene glycol monoethyl ether, Esters such as ethyl acetate and acetic acid esterification products of the above glycol ethers,
Examples include alcohols such as ethylene glycol and propylene glycol, aliphatic hydrocarbons such as octane, and petroleum solvents such as petroleum naphtha and solvent naphtha.

The above-mentioned diluents are used alone or as a mixture of two or more kinds, and the preferable range of the amount used is 10 to 250 relative to 100 parts by weight of the photosensitive resin (A).
Parts by weight, preferably 30 to 200 parts by weight.

The photosensitive resin composition of the present invention may be used in combination with other thermosetting resins or thermosetting monomers in order to further improve the physical properties thereof. For example, an epoxy compound, a block isocyanate, a melamine resin, a urea resin, a maleimide resin, a cyanate resin, an unsaturated polyester resin, a diallyl (iso) phthalate resin, an oxazoline compound or the like can be added and used. Particularly when the photosensitive resin composition of the present invention is used as a resist ink, the physical properties can be improved by adding an epoxy compound. Epoxy resins generally known as epoxy compounds, for example, bisphenol-A
Type epoxy resin, bisphenol-F type epoxy resin,
Bisphenol-S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol-A-novolac type epoxy resin, naphthalene type epoxy resin, naphthalene novolac type epoxy resin, biphenol type epoxy resin Resins, bixylenol type epoxy resins, triglycidyl isocyanurate, etc. are used, and compounds obtained by adding acrylic acid to a part of the epoxy groups in these epoxy resins and acrylic group-containing epoxy compounds (Kanekaresin AXE ) Etc. can also be used.

An epoxy curing agent may be added to the composition of the present invention. As the curing agent, dicyandiamide or a derivative thereof, melamines, imidazoles, amines, thiols, acid anhydrides, hydrazides, etc., which are known and commonly used, are appropriately selected and used according to the purpose. . These may be used alone or in combination of two or more.

Further, in the present invention, other known and commonly used additives may be added and used. For example, as an inorganic filler, known conventional materials such as barium sulfate, barium titanate, silicon oxide powder, finely powdered silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder. Can be used. Further, if necessary, phthalocyanine blue, phthalocyanine green, iodin green
Well known conventional colorants such as hydroquinone, hydroquinone monomethyl ether and phenothiazine, asbestos, olben, and benton. And other commonly used thickeners, silicone-based, fluorine-based, polymer-based, etc. defoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based, silane coupling agents Known conventional additives such as adhesion promoters can be used.

The photosensitive resin composition of the present invention can be used not only as a resist ink but also in other forms such as a dry film resist. In addition to the solder resist, it can also be used for applications such as etching resist and marking ink. When the photosensitive resin composition of the present invention is used as a resist ink, A) (1) a compound having two or more carboxylic acid anhydride groups, and (2) 0.1% of the carboxylic acid anhydride group. ~ 1.0
A photosensitive resin obtained by reacting an equal amount of radically polymerizable amine and (3) an equivalent amount of radically polymerizable active hydrogen compound with 0.0 to 0.9 to the carboxylic acid anhydride group, and B) photopolymerization Initiator C) Reactive and / or non-reactive diluent components and, if necessary, epoxy resin, filler, pigment,
Add three-roll mill, ball
It is used after being thoroughly mixed with an appropriate device such as a rumill to prepare an ink. Such a resist ink composition may be applied to a circuit-formed printed wiring board, for example, by screen printing, a cartridge coater, a roll coater, a spray coater, or the like, in whole or in part. A coating film can be formed by a method such as applying to After that, direct irradiation of laser light or through a photomask on which a pattern is formed is selectively exposed to actinic rays such as a high pressure mercury lamp or a metal halide lamp, and the unexposed portion is developed with a developing solution to form a pattern. Can be formed. After exposure, as a developing solution for forming a resist pattern, an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. can be used. . After development, in order to improve the physical properties, heating and / or light irradiation may be further added. In particular, by heating at 100 to 200 ° C. for 5 to 90 minutes, curing of the resin proceeds and the effects of the invention are sufficiently exhibited.

[0022]

EXAMPLES The present invention will be specifically described below with reference to production examples and examples, but the present invention is not limited thereto. The terms "part" and "%" are based on weight unless otherwise specified.

[0023]

[Production Example 1] 100 parts of SMA1000 (styrene-maleic anhydride copolymer resin, styrene: maleic anhydride = 1: 1, manufactured by A-Chemicals) and carbitol acetate were placed in a reactor equipped with a cooling pipe, a stirring device and a thermometer. 10
0 part was added, and the mixture was stirred by heating at 80 ° C. to uniformly dissolve it. A mixed solution of 31.2 parts of diallylamine and 31.2 parts of carbitol acetate was added dropwise to this solution over 30 minutes. After the dropwise addition was completed, stirring was continued for another 3 hours and then allowed to cool to obtain 262.4 parts of a photosensitive resin solution having a solid content of 50%.
The acid value of this product was 136 mgKOH / g.

[0024]

[Manufacturing Example 2] 100 parts of SMA and 100 parts of carbitol acetate were placed in a reactor equipped with a cooling tube, a stirring device, and a thermometer, and heated at 100 ° C. and stirred to uniformly dissolve them. A mixed solution of 48 parts of diallylamine and 48 parts of carbitol acetate was added dropwise to this solution over 30 minutes. After the dropwise addition was completed, stirring was continued for another 3 hours and then allowed to cool to obtain 296 parts of a photosensitive resin solution having a solid content of 50%. The acid value of this product was 94 mgKOH / g.

[0025]

[Production Example 3] 112.4 parts of SMA2000 (styrene-maleic anhydride copolymer resin, styrene: maleic anhydride = 2: 1, manufactured by A-Chemical Chemicals) was added to a reactor equipped with a cooling pipe, a stirrer and a thermometer. 112.4 parts of tall acetate was added, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve it. To this solution, a mixed solution of 35.6 parts of diallylamine and 35.6 parts of carbitol acetate was added dropwise over 30 minutes. After the dropwise addition was completed, stirring was continued for another 3 hours and then allowed to cool to obtain 296 parts of a photosensitive resin solution having a solid content of 50%. The acid value of this product was 68 mgKOH / g.

[0026]

[Production Example 4] SMA2000, 40.44 parts and carbitol acetate 33.09 parts were put into a reactor equipped with a cooling tube, a stirring device and a thermometer, and heated and stirred at 100 ° C to uniformly dissolve them. A mixed solution of 9.72 parts of diallylamine and 1.49 parts of carbitol acetate was added dropwise to this solution over 30 minutes. After the dropwise addition was completed, stirring was continued for 1 hour, and then a mixed solution of 1.71 parts of allylamine and 17.29 parts of carbitol acetate was added dropwise over 30 minutes. After stirring for an additional 1 hour, let cool to a solid content of 50.
% 296 parts of a photosensitive resin solution was obtained. The acid value of this product was 71 mgKOH / g.

[0027]

[Production Example 5] SMA1440 (styrene-maleic anhydride copolymer resin, styrene-maleic anhydride = 1: 1, manufactured by A-Chemical Chemical Co., Ltd.) was mixed with butyl cellosolve 35 in a reactor equipped with a cooling pipe, a stirring device and a thermometer. .About.50% added product) (48.1 parts) and carbitol acetate (25.9 parts) were added, and the mixture was heated and stirred at 80 ° C. to dissolve uniformly. 9.98 of diallylamine in this solution
30 parts of a mixture of 5 parts and carbitol acetate 5.37 parts
It dripped over minutes. After the dropwise addition was completed, stirring was continued for another 2 hours and then allowed to cool to obtain a photosensitive resin solution having a solid content of 65% 89.
35 parts were obtained. The acid value of this product was 97 mgKOH / g.

[0028]

COMPARATIVE MANUFACTURING EXAMPLE 1 SMA 1000, 40.4 parts and carbitol acetate 50 parts were placed in a reactor equipped with a cooling tube, a stirrer and a thermometer, and heated and stirred at 110 ° C. to uniformly dissolve them. To this solution was added 5 parts of 2-hydroxyethyl acrylate, and the reaction was carried out while blowing air. After stirring for 18 hours, let it cool down to a solid content of 5
95.4 parts of 0% photosensitive resin solution was obtained. The acid value of this product was 101 mgKOH / g.

[0029]

[Comparative Production Example 2] A cresol novolac type epoxy resin having an epoxy equivalent of 214 in a reactor equipped with a cooling pipe, a stirring device, and a thermometer (Epiclon N manufactured by Dainippon Ink
-680) 107 parts, carbitol acetate 62 parts,
30 parts of solvent naphtha was added, and the mixture was heated and stirred at 90 ° C. to uniformly dissolve it. 40 parts of acrylic acid, 0.1 part of hydroquinone and 0.6 part of dimethylbenzylamine were added to this solution.
8 parts was added, and the mixture was reacted at 110 ° C. for 24 hours while blowing air. After cooling the reaction mixture to 100 ° C,
Tetrahydrophthalic anhydride (37 parts) was added, and stirring was continued for 4 hours to obtain 240 parts of a photosensitive resin solution having a solid content of 62%. The acid value of this product was 50 mgKOH / g.

[0030]

Example 1 Resin obtained in Production Example 1 50 parts Dipentaerythritol hexaacrylate 4 parts Irgacure 907 (CIBA-GEIGY photopolymerization initiator) 5 parts YX-4000 (oil resin epoxy epoxy resin) 13 parts Barium sulphate 25 parts Phthalocyanine lean 1 part Dicyandiamide 1 part Florene AC-326F (Kyoeisha Oil & Fat Defoamer) 1 part After pre-kneading the above ingredients, knead them with a 3-roll mill,
A photosensitive resin composition was prepared. This photosensitive resin composition is applied to the entire surface of a printed circuit board by a screen printing method,
A test piece was prepared.

[0031]

Example 2 Resin obtained in Production Example 2 50 parts Dipentaerythritol hexaacrylate 5 parts Irgacure 907 5 parts Diethylthioxanthone 2 parts Triglycidyl isocyanurate 10 parts Silica 5 parts Barium sulfate 20 parts Phthalocyanine dry 1 part Dicyandiamide 1 part Florene AC-326F 1 part The above compounding ingredients were kneaded and applied in the same manner as in Example 1 to prepare test pieces.

[0032]

Example 3 Resin obtained in Production Example 2 20 parts Resin obtained in Production Example 3 30 parts Dipentaerythritol hexaacrylate 5 parts Irgacure 907 5 parts Triglycidyl isocyanurate 10 parts Barium sulfate 25 parts Phthalocyanine 1 part Floren AC-326F 2 parts Solvent naphtha 2 parts The above compounding ingredients were kneaded and applied in the same manner as in Example 1 to prepare test pieces.

[0033]

Example 4 Resin obtained in Production Example 4 60 parts Dipentaerythritol hexaacrylate 5 parts Irgacure907 5 parts YX-4000 10 parts Barium sulphate 15 parts Phthalocyanine lin 1 part Dicyandiamide 2 parts Florene AC -326F 2 parts The above compounding ingredients were kneaded and coated in the same manner as in Example 1 to prepare a test piece.

[0034]

Example 5 Resin Obtained in Production Example 50 50 parts Dipentaerythritol hexaacrylate 5 parts Irgacure 907 5 parts YX-4000 15 parts Barium sulfate 20 parts Phthalocyanine lin 1 part Dicyandiamide 2 parts Florene AC -326F 2 parts The above compounding ingredients were kneaded and coated in the same manner as in Example 1 to prepare a test piece.

[0035]

Comparative Example 1 Resin obtained in Comparative Production Example 1 50 parts Dipentaerythritol Hexaacrylate 4 parts Irgacure907 5 parts YX-4000 (Epoxy resin made of oiled shell epoxy) 13 parts Barium sulfate 25 parts Phthalocyanine grease 1 part Dicyandiamide 1 part Florene AC-326F (anti-foaming agent manufactured by Kyoeisha Oil and Fat) 1 part The above compounding ingredients were kneaded and applied in the same manner as in Example 1 to prepare test pieces.

[0036]

Comparative Example 2 Resin obtained in Comparative Production Example 1 50 parts Dipentaerythritol hexaacrylate 5 parts Irgacure907 5 parts Diethylthioxanthone 2 parts Triglycidyl isocyanurate 10 parts Silica 5 parts Barium sulfate 20 parts Phthalocyanine glycol 1 part Dicyandiamide 1 part Florene AC-326F 1 part The above compounding ingredients were kneaded and applied in the same manner as in Example 1 to prepare test pieces.

[0037]

Comparative Example 3 Resin obtained in Comparative Production Example 2 50 parts Dipentaerythritol hexaacrylate 4 parts Irgacure907 5 parts YX-4000 (epoxy resin made of oiled shell epoxy) 13 parts Barium sulfate 25 parts Phthalocyanine grease 1 part Dicyandiamide 1 part Florene AC-326F (anti-foaming agent manufactured by Kyoeisha Oil and Fat) 1 part The above compounding ingredients were kneaded and applied in the same manner as in Example 1 to prepare test pieces.

The test pieces obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated as follows.

1) Finger touch dryness test Each test piece was placed in a hot air circulation oven, dried at 80 ° C. for 20 minutes, cooled to room temperature, and touched with a finger to determine the tack of the coating film and evaluate it. ◎: No tack is observed ○: Slight tack is observed △: Remarkable tack is observed ×: Ink is adhered to fingers Next, the photomask on which the pattern is formed is applied to the coating surface And was irradiated with ultraviolet rays of 500 mJ / cm 2 using a metal halide lamp manufactured by Oak Manufacturing Co., Ltd. Next, using 1% sodium carbonate aqueous solution as a developing solution, development was carried out for 1 minute, washing with water and drying. Next, put in a hot air circulation furnace heated to 150 ° C.
Post-cure was performed for a minute to prepare a test piece.

2) Adhesion test The test piece obtained by the above method was JIS
According to the test method of D 0202, cross-cuts were put in a grid pattern, and then the number of peeled grid patterns after the peeling test with cellophane tape was observed. ◯; 100/100 Δ; 50/100 to 99/100 ×; 0/100 to 49/100

3) Pencil hardness test Each of the same test pieces as in the adhesion test is JIS K
Hardness was measured according to the test method of 5400.

4) Solder resistance test JIS C C
According to the test method of 6481, the state and adhesiveness of the coating film after immersion in a solder bath at 260 ° C. for 15 seconds each were determined, and the maximum number of immersions that did not cause an abnormality was used as an index of heat resistance.

5) Plating resistance Using the same test pieces as those used in the adhesion test, an electroless nickel plating solution ICP Nicoron manufactured by Okuno Seiyaku Kogyo was used.
After plating for 15 minutes at a liquid temperature of 85 ° C., the coating film was peeled with a cellophane tape to evaluate the peeling condition. Furthermore, the electroless gold plating solution OPC made by Okuno Seiyaku Kogyo
Using Muden Gold AD, plating was performed for 20 minutes at a liquid temperature of 90 ° C., and the state of the coating film was similarly evaluated.

6) Insulation Resistance Test Using JIS Z 3197, type 2 G-10 type comb test pattern, a test piece was prepared under the same conditions as in the adhesion test, and after applying 100 V for 1 minute. The insulation resistance was measured.

Table 1 shows the results of the tests 1) to 6) performed on the test pieces obtained in Examples 1 to 5 and Comparative Examples 1 to 3. It is clear from the table that the resist ink to which the photosensitive resin composition of the present invention is applied is excellent.

[0046]

[Table 1]

[0047]

As described above, since the photosensitive resin composition of the present invention is excellent in heat resistance and chemical resistance, it is difficult to apply solder resist heat and plating, which have been difficult in the past especially when applied to resist ink. It is possible to achieve both of these, and the workability is good. Further, from these properties, it can be said to be useful in a wide range of applications such as other paints, adhesives, inks and printing plates.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08F 290/00 MRM 7442-4J C09D 11/00 PTE G03F 7/027 H01B 3/30 M 9059-5G H05K 3/06 H // H01B 7/34 A 7244-5G (72) Inventor Yuuki Miyazawa 1-1, Suzuki-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Ajinomoto Co., Inc. Central Research Laboratory (72) Inventor, Hiroyuki Sakata Kanagawa Ajinomoto Co., Inc. Central Research Laboratory 1-1, Suzuki-cho, Kawasaki-ku, Kawasaki Prefecture

Claims (5)

[Claims] 1. A) (1) a compound having two or more carboxylic acid anhydride groups, and (2) 0.1 to 1.0 equivalent of primary and / or 2 equivalents to the carboxylic acid anhydride groups. A compound having a primary amine and a radical polymerizable group, and (3) having 0.0 to 0.9 equivalents of active hydrogen other than a primary or secondary amine and a radical polymerizable group with respect to the carboxylic acid anhydride group. Alternatively, a photosensitive resin composition obtained by reacting with a compound which does not have it and B) a photopolymerization initiator as an essential component. 2. A) (1) a compound having two or more carboxylic acid anhydride groups, and (2) 0.1 to 1.0 equivalent of primary and / or 2 equivalents to the carboxylic acid anhydride groups. A compound having a primary amine and a radical polymerizable group, and (3) a compound having an active hydrogen and a radical polymerizable group other than the primary or secondary amine in an amount of 0.0 to 0.9 equivalent to the carboxylic acid anhydride group A resist ink composition containing as an essential component a photosensitive resin obtained by reacting with, B) a photopolymerization initiator, and C) a reactive and / or non-reactive diluent. 3. A copolymer obtained by reacting 10 mol% or more of maleic anhydride with 90 mol% or less of a radical-polymerizable monomer other than maleic anhydride, wherein the compound having two or more carboxylic acid anhydride groups. The photosensitive resin composition according to any one of claims 1 to 2. 4. The photosensitive resin composition according to claim 1, wherein the compound having a primary and / or secondary amine and a radical polymerizable group is allylamine or diallylamine. 5. The photosensitive resin is maleic anhydride 10-90.
0.1 to 1.0 equivalent of diallylamine and / or allylamine with respect to the carboxylic acid anhydride group in the compound having the carboxylic acid anhydride group, which is a copolymer of 90% to 10% by mol of styrene. And a molecular weight of 600 to 30, which is obtained by reacting 0.0 to 0.6 equivalent of a monohydric alcohol having 10 or less carbon atoms with alcoholic active hydrogen.
3. The photosensitive resin composition according to claim 1, which is 000.