JP2011144230A - Polyfunctional epoxy (meth)acrylate compound and photosensitive thermosetting resin composition comprising the compound, and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyfunctional epoxy (meth)acrylate compound that achieves an excellent cured film, and to provide a photosensitive thermosetting resin composition comprising the polyfunctional epoxy (meth)acrylate compound. <P>SOLUTION: The polyfunctional epoxy (meth)acrylate compound (A) is obtained by causing a polybasic acid anhydride (d) to react with a reaction product of a compound (a) containing at least two epoxy groups in one molecule, (meth)acrylic acid anhydride (b) and an unsaturated group-containing monocarboxylic acid (c), and is represented by the general formula (wherein X is a bivalent aromatic group and/or an alkyl group and/or a cyclohexyl group; Y is a bivalent aromatic residue or a dicarboxylic acid residue; at least one of M's is a carboxylic acid residue of reacted (meth)acrylic acid anhydride and at least one of M's is a residue of a polybasic acid anhydride, containing at least one carboxy group, and the balance comprising a hydrogen atom; Q is a (meth)acrylic acid residue formed by a reaction of (meth)acrylic acid anhydride with a hydroxy group or a residue of an unsaturated group-containing monocarboxylic acid; and m is 0-100). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polyfunctional epoxy (meth) acrylate compound, a photosensitive thermosetting resin composition containing the compound, and a cured product thereof.

  Currently, printed wiring boards are manufactured by soldering for the purpose of protecting solder from adhering to unnecessary parts when electronic components are mounted on a printed wiring board by soldering after forming a wiring (circuit) pattern. A protective layer called a mask is coated.

  Solder resist used in the manufacture of printed wiring boards for IC packages such as BGA and CSP using consumer and industrial printed wiring boards and sealing resins is UV curable, thermosetting or UV curable and thermosetting. A liquid solder resist ink to be used together is applied to the printed wiring board by a printing method such as screen printing, or a dry film resist that does not contain an organic solvent, such as a polyester film or polyethylene film, is applied to the printed wiring board. There is a type that obtains a film by peeling off the support, but in recent years, the type that uses both UV curing and heat curing is the mainstream from the viewpoint of high accuracy and high density, and after photocuring by UV irradiation (temporary curing) Develop with a dilute alkaline aqueous solution to form an image and heat to finish and harden the skin. The are obtained.

  Resist ink containing phenolic novolac acid-modified epoxy acrylate compound and epoxy compound as essential components as a commercially available alkali development type solder resist for the above-mentioned printed wiring board for IC package (for example, see Patent Documents 1 and 2) When the coating is applied, the cured film may be discolored or cracked during various plating applications during package mounting, and cracks may also occur in the cured film during the PCT test (humidification test), which is one of the long-term reliability tests. There is a problem with the crack resistance that occurs, and there is a need for improvement. Such a problem is not limited to the case of the above-described mounting technique, and is not desirable in a solder resist of a general printed wiring board.

  Various attempts have been made to deal with such problems. For example, a reaction product obtained by reacting a novolac type epoxy compound with a phenol compound and / or a naphthol compound and an unsaturated group-containing monocarboxylic acid and further reacting with a polybasic acid anhydride, and a resist ink containing the epoxy compound as an essential component (For example, refer to Patent Documents 3 and 4). Although this resist ink provides flexibility to the cured film to be formed and crack resistance is solved, there is a problem that alkali developability is not sufficient and it becomes difficult to form a clear image of the resist pattern. Yes. Also, an epoxy compound selected from a bisphenol F-type epoxy compound or rubber-modified epoxy and an unsaturated group-containing monocarboxylic acid are reacted, and a reaction product obtained by reacting a polybasic acid anhydride and an epoxy compound are essential components. Resist ink (see, for example, Patent Document 5), a reaction product obtained by reacting a bisphenol polyfunctional epoxy compound having a specific structure with an unsaturated group-containing monocarboxylic acid, and further reacting with a polybasic acid anhydride, and an epoxy There is a resist ink containing a compound as an essential component (see, for example, Patent Document 6). Although these resist inks provide flexibility to the cured film to be formed and crack resistance has been solved, since the sensitivity to ultraviolet rays (light) is low, the resolution of the formed image is low, In recent years, there is a concern that the high-density packaging required in the next generation cannot be sufficiently handled.

  Furthermore, a reaction product obtained by reacting a novolak-type epoxy compound and / or glycol-based epoxy compound, an unsaturated group-containing monocarboxylic acid and a saturated monocarboxylic acid, and further reacting with a polybasic acid anhydride, and an epoxy compound are essential components. Resist ink (for example, refer to Patent Document 7), epoxy compound, compound having one alcoholic hydroxyl group and one functional group selected from carboxyl group and amino group in one molecule, and unsaturated group-containing monocarboxylic acid There is a reaction product obtained by reacting a polybasic acid anhydride with a polybasic acid anhydride (see, for example, Patent Document 8).

  Furthermore, the reaction product of an acid anhydride of tribasic acid or more and 2-hydroxyethyl (meth) acrylate alone or a mixture of it and (meth) acrylic acid is added to an epoxy resin or epoxy so that the carboxyl group remains unreacted. There is a reaction product reacted with (meth) acrylate (for example, Patent Documents 9 and 10).

JP-A 61-243869 Japanese Patent Laid-Open No. 3-253093 Japanese Patent Laid-Open No. 11-288091 Japanese Patent Laid-Open No. 11-315107 JP-A-11-242331 JP 2001-278947 A JP 2000-321765 A JP 2002-90994 A JP-A-4-170480 Japanese Patent Laid-Open No. 4-170481

  However, the inventions described in the above-mentioned patent documents are one of long-term reliability tests as well as crack resistance, although flexibility is imparted to the cured film to be formed and crack resistance is solved. PCT (pressure cooker test) resistance is not sufficient, development life in the solvent drying process of the film is remarkably short, and it is difficult to form a wiring pattern on a printed wiring board. Furthermore, when a large amount of saturated monocarboxylic acid is blended in the reaction in order to adjust the degree of flexibility in Patent Document 7, there is a problem that the dryness to touch after the solvent drying process of the film is remarkably lowered. In Patent Document 9, problems such as the need for an expensive microencapsulated thermosetting catalyst are required to maintain the development life.

  Thus, when flexibility is imparted to a cured film formed to solve crack resistance, generally either alkali developability or PCT resistance is greatly reduced, and further, the development life in the solvent drying step And the dryness of the touch after the solvent drying process is the basic performance as a solder resist ink used in the manufacture of printed wiring boards for semiconductor packages. Balances PCT resistance, solder heat resistance, adhesion to substrates, plating properties, electrical insulation, etc. in a well-balanced manner and completely eliminates the problem of cracks in the cured film that occurs during mounting and thermal cycle testing of long-term reliability tests. It is extremely difficult to solve, and there is nothing that has been fully satisfied so far.

  An object of the present invention is to provide a polyfunctional epoxy (meth) acrylate compound capable of achieving an excellent cured film and a photosensitive thermosetting resin composition containing the polyfunctional epoxy (meth) acrylate compound. It is in.

  As a result of intensive studies to solve the above-described problems, the present inventors have found an epoxy (meth) acrylate compound having a new structure suitable for achieving the above-described object, and the epoxy (meta) ) A photosensitive thermosetting resin composition in which an epoxy compound, a photopolymerization initiator, and a diluent are blended as essential components in an acrylate compound exhibits a well-balanced characteristic with respect to a wide variety of necessary characteristics as described above. And it discovered that the hardened | cured film formed formed the hardened | cured material which was remarkably excellent in PCT tolerance and plating tolerance, and completed this invention.

に示すことを特徴とする。（式中、Ｘは二価の芳香族基及び／又はアルキル基及び／又はシクロヘキシル基、Ｙは二価の芳香族残基、ジカルボン酸残基を表す。Ｍは少なくとも１つは、（メタ）アクリル酸無水物が反応したカルボン酸残基であり、又少なくとも１つは、カルボキシル基を1個以上含有する多塩基酸無水物の残基であり、残りは水素原子を表す。Ｑは（メタ）アクリル酸無水物が水酸基と反応して生成する（メタ）アクリル酸の残基、及び不飽和基含有モノカルボン酸の残基を表す。ｍは、０〜１００である。） That is, the polyfunctional epoxy (meth) acrylate compound (A) of the present invention includes a compound (a) having at least two epoxy groups in one molecule, (meth) acrylic anhydride (b), and an unsaturated group. A polybasic acid anhydride (d) was further reacted with the reaction product of the monocarboxylic acid (c) contained in the following general formula:

It is characterized by the following. (In the formula, X represents a divalent aromatic group and / or an alkyl group and / or a cyclohexyl group, Y represents a divalent aromatic residue, and a dicarboxylic acid residue. M represents at least one of (meth) A carboxylic acid residue reacted with acrylic anhydride, and at least one is a residue of a polybasic acid anhydride containing one or more carboxyl groups, and the remainder represents a hydrogen atom. ) Represents a residue of (meth) acrylic acid produced by reaction of an acrylic anhydride with a hydroxyl group and a residue of an unsaturated group-containing monocarboxylic acid, where m is 0 to 100.)

  In a preferred embodiment of the compound of the present invention, the polyfunctional epoxy (meth) acrylate compound (A) has an acid value in the range of 60 to 110 mgKOH / g.

  In a preferred embodiment of the compound of the present invention, the polyfunctional epoxy (meth) acrylate compound according to claim 2, wherein 95% or more of the acid value is derived from a carboxyl group derived from a polybasic acid anhydride. (A).

  The photosensitive thermosetting resin composition of the present invention includes the polyfunctional epoxy (meth) acrylate compound (A) of the present invention, an epoxy compound (B) having two or more epoxy groups in one molecule, and a photopolymerization initiator. It contains (C) and diluent (D) as essential components.

  The cured product of the present invention is obtained by curing the photosensitive thermosetting resin composition of the present invention.

（式中、Ｘは二価の芳香族基及び／又はアルキル基及び／又はシクロヘキシル基、Ｙは二価の芳香族残基、ジカルボン酸残基を表す。Ｍは少なくとも１つは、（メタ）アクリル酸無水物が反応したカルボン酸残基であり、又少なくとも１つは、カルボキシル基を1個以上含有する多塩基酸無水物の残基であり、残りは水素原子を表す。Ｑは（メタ）アクリル酸無水物が水酸基と反応して生成する（メタ）アクリル酸の残基、及び不飽和基含有モノカルボン酸の残基を表す。ｍは、０〜１００である。）で表されることを特徴とする。 The polyfunctional epoxy (meth) acrylate compound of the present invention has the general formula [Chemical Formula 2]:

(In the formula, X represents a divalent aromatic group and / or an alkyl group and / or a cyclohexyl group, Y represents a divalent aromatic residue, and a dicarboxylic acid residue. M represents at least one of (meth) A carboxylic acid residue reacted with acrylic anhydride, and at least one is a residue of a polybasic acid anhydride containing one or more carboxyl groups, and the remainder represents a hydrogen atom. ) Represents a residue of (meth) acrylic acid generated by reaction of an acrylic anhydride with a hydroxyl group and a residue of an unsaturated group-containing monocarboxylic acid, where m is 0 to 100. It is characterized by that.

  The polyfunctional epoxy (meth) acrylate compound (A) in the present invention has a photosensitive double bond and a carboxyl group capable of radical polymerization in the molecule, and is subjected to a photopolymerization initiator under ultraviolet (light) irradiation. Radiation polymerization forms a cured product (temporary curing), and the part not exposed to light is excellent in alkali developability, which is removed with a dilute alkaline solution, and the carboxyl group present in the cured product is a heat curing process (finishing) It has an advantageous effect that an excellent cured film can be obtained by reacting with the epoxy compound (B) coexisting in curing to form a strong bond.

  The photosensitive thermosetting resin composition containing the polyfunctional epoxy (meth) acrylate compound of the present invention has an excellent balance of dryness to touch, alkali developability and sensitivity to ultraviolet rays, and adhesion necessary as a resist coating film. In addition, there is an advantageous effect that an excellent cured coating film can be provided at a high level in solder heat resistance and PCT resistance. Therefore, there is an advantageous effect that it is optimal as a material for manufacturing printed wiring boards, particularly IC packages such as BGA (Bold Grit Array) and CSP (Chip Scale Package).

The nuclear magnetic resonance spectrum of the polyfunctional epoxy acrylate compound obtained in Synthesis Example 1 is shown. The infrared absorption spectrum of the polyfunctional epoxy acrylate compound obtained in Synthesis Example 1 is shown.

  An example of the present invention will be described below. First, in this specification, (meth) acrylic anhydride is acrylic anhydride, methacrylic anhydride or a mixture thereof, and (meth) acrylic acid is acrylic acid, methacrylic acid or a mixture thereof. And epoxy (meth) acrylate means epoxy acrylate, epoxy methacrylate, or a mixture thereof. In addition, the photosensitive thermosetting resin composition may be simply referred to as “curable resin composition”.

で表される。 The polyfunctional epoxy (meth) acrylate compound of the present invention has the general formula [Chemical Formula 3]:

It is represented by

  In the formula, X represents a divalent aromatic group and / or an alkyl group and / or a cyclohexyl group, and Y represents a divalent aromatic residue or a dicarboxylic acid residue. M is at least one carboxylic acid residue reacted with (meth) acrylic anhydride, and at least one is a polybasic acid anhydride residue containing one or more carboxyl groups, and the rest Represents a hydrogen atom. Q represents a residue of (meth) acrylic acid produced by the reaction of (meth) acrylic anhydride with a hydroxyl group and a residue of an unsaturated group-containing monocarboxylic acid. n can be 0 to 100, and m can be 0 to 100.

で表される。 The polyfunctional epoxy (meth) acrylate compound of the present invention has the general formula [Chemical Formula 4]:

It is represented by

  In the formula, X represents a divalent aromatic group and / or an alkyl group and / or a cyclohexyl group, and Y represents a divalent aromatic residue or a dicarboxylic acid residue. M is at least one carboxylic acid residue reacted with (meth) acrylic anhydride, and at least one is a polybasic acid anhydride residue containing one or more carboxyl groups, and the rest Represents a hydrogen atom. Q represents a residue of (meth) acrylic acid produced by the reaction of (meth) acrylic anhydride with a hydroxyl group and a residue of an unsaturated group-containing monocarboxylic acid. n can be 0-100, and m can be 0-100.

  In the present invention, an epoxy compound (a) containing two or more epoxy groups in one molecule is reacted with a (meth) acrylic anhydride (b) and an unsaturated group-containing monocarboxylic acid (c). A polyfunctional epoxy (meth) acrylate compound obtained by further reacting the resulting reaction product with a polybasic acid anhydride (d), and the acid-modified epoxy (meth) acrylate compound (A), in one molecule Photosensitive thermosetting resin composition containing epoxy compound (B) having two or more epoxy groups, photopolymerization initiator (C), diluent (D) as essential components, and the photosensitive thermosetting resin The present invention provides a cured product having excellent cured film characteristics obtained by curing the composition.

、又は一般式[化６]：

に示すことを特徴とする。（式中、Ｘは二価の芳香族基及び／又はアルキル基及び／又はシクロヘキシル基、Ｙは二価の芳香族残基、ジカルボン酸残基を表す。Ｍは少なくとも１つは、（メタ）アクリル酸無水物が反応したカルボン酸残基であり、又少なくとも１つは、カルボキシル基を1個以上含有する多塩基酸無水物の残基であり、残りは水素原子を表す。Ｑは（メタ）アクリル酸無水物が水酸基と反応して生成する（メタ）アクリル酸の残基、及び不飽和基含有モノカルボン酸の残基を表す。ｎは０〜１００、ｍは、０〜１００である。） First, the polyfunctional epoxy (meth) acrylate compound (A) in this invention is demonstrated. The polyfunctional epoxy (meth) acrylate compound (A) of the present invention comprises a compound (a) having at least two epoxy groups in one molecule, a (meth) acrylic anhydride (b), and an unsaturated group-containing mono The reaction product of carboxylic acid (c) is further reacted with polybasic acid anhydride (d):

Or the general formula [Formula 6]:

It is characterized by the following. (In the formula, X represents a divalent aromatic group and / or an alkyl group and / or a cyclohexyl group, Y represents a divalent aromatic residue, and a dicarboxylic acid residue. M represents at least one of (meth) A carboxylic acid residue reacted with acrylic anhydride, and at least one is a residue of a polybasic acid anhydride containing one or more carboxyl groups, and the remainder represents a hydrogen atom. ) Represents a residue of (meth) acrylic acid and an unsaturated group-containing monocarboxylic acid produced by the reaction of an acrylic anhydride with a hydroxyl group, where n is 0 to 100 and m is 0 to 100. .)

  The polyfunctional epoxy (meth) acrylate compound (A) is composed of an epoxy compound (a) having two or more epoxy groups in one molecule, (meth) acrylic anhydride (b), and an unsaturated group-containing monocarboxylic acid. The acid (c) is added in the presence or absence of a known catalyst and a polymerization inhibitor described below, in an inert gas stream or air, and in the presence or absence of a diluent described below, 60 to 150 ° C. To obtain a reaction product having a secondary alcoholic hydroxyl group and an unsaturated group in the molecule, and further adding a polybasic acid anhydride (d) to the alcoholic hydroxyl group remaining in the reaction product at 30 to 150 ° C. It can obtain by making it react.

The reaction of the epoxy compound (a) having two epoxy groups in one molecule, the (meth) acrylic anhydride (b), and the unsaturated group-containing monocarboxylic acid (c) can be traced according to JIS.
The acid value (mgKOH / g) described in K6901 was confirmed by measurement. Also, a reaction product of an epoxy compound (a) having two or more epoxy groups in one molecule, (meth) acrylic anhydride (b) and an unsaturated group-containing monocarboxylic acid (c), and a polybasic acid The reaction with the anhydride (d) was traced and confirmed by the presence or absence of an absorption wavelength (1780 cm ⁻¹ ) peculiar to the acid anhydride and the acid value measurement from IR measurement.

  Although it does not specifically limit as an epoxy compound (a) which has two or more epoxy groups in 1 molecule used when synthesize | combining the said epoxy (meth) acrylate compound (A), 2 or more in 1 molecule An epoxy compound that can be obtained by epoxidizing epichlorohydrin by a known method with phenols, carboxylic acids, glycols, or amines having active hydrogen, alone or in combination of two or more, in one molecule Phenols, carboxylic acids, glycols, or amines having two active hydrogens are epoxidized with epichlorohydrin by a known method, alone or in combination of two or more, and secondary alcoholic hydroxyl groups in the molecule In a molecule obtained by epoxidation with epichlorohydrin by a known method. Epoxy compounds having the above epoxy groups, phenol novolaks having 3 or more phenolic hydroxyl groups in one molecule obtained by addition-condensation of phenols such as phenol and cresol with formaldehyde can be epoxyized with epichlorohydrin by a known method. An epoxy compound having three or more epoxy groups in one molecule obtained by the conversion, an epoxy compound having two epoxy groups in one molecule and dicarboxylic acids having two active hydrogens, an unsaturated group-containing dicarboxylic acid Examples include epoxy compounds obtained by reacting either acids or phenols.

  A general commercial item can also be used for the epoxy compound (a) which has a 2 or more epoxy group in 1 molecule. Examples of commercially available products include “Epicoat 828”, “Epicoat 834”, “Epicoat 1001” and “Epicoat 1004” manufactured by Japan Epoxy Resin Co., Ltd., and “Epicron 840” manufactured by Dainippon Ink & Chemicals, Inc. “Epicron 850”, “Epicron 1050”, “Epicron 2055”, trade names “Epototo 128” manufactured by Tohto Kasei Co., Ltd., trade names “D.E.R. 317”, “D.E.R. .331 ”,“ D.E.R.661 ”,“ D.E.R.664 ”, trade names“ Araldite 250 ”,“ Araldite 260 ”,“ Araldite 2600 ”manufactured by Asahi Kasei Kogyo Co., Ltd., Sumitomo Chemical Co., Ltd. Bisphenols such as “Sumiepoxy ESA-011”, “Sumiepoxy ESA-014”, “Sumiepoxy ELA-128” Type A epoxy compound, trade name “Epicron 830S” manufactured by Dainippon Ink & Chemicals, Inc., product name “Epicoat 807” manufactured by Japan Epoxy Resin Co., Ltd., trade names “Epototo YDF-170”, “Epototo YDF-” manufactured by Tohto Kasei Co., Ltd. 175 ”,“ Epototo YDF-2004 ”,“ Araldite XPY306 ”manufactured by Asahi Kasei Kogyo Co., Ltd., Nippon Kayaku product name“ EBPS-200 ”, Asahi Denka Kogyo product name“ EPX ” -30 ", bisphenol S-type epoxy compounds such as Dainippon Ink & Chemicals' brand name" Epicron EXA1514 ", bisphenol fluorene-type epoxy compounds such as Osaka Gas's brand name" BPFG ", Japan Epoxy Resin Product names “YL-6056”, “YL-6021”, “YX-4” 00 ”,“ YX-4000H ”and other bixylenol type or biphenyl type epoxy compounds, or mixtures thereof, trade names“ Epototo ST-2004 ”,“ ST-2007 ”,“ ST-3000 ”manufactured by Tohto Kasei Co., Ltd. Hydrogenated bisphenol A type epoxy compounds such as “Epicoat 152” and “Epicoat 154” manufactured by Japan Epoxy Resin Co., Ltd., and “D.E.N. 431” and “D.E. N.438 ”, trade names“ Epicron N-690 ”,“ Epicron N-695 ”,“ Epicron N-730 ”,“ Epicron N-770 ”,“ Epicron N-865 ”, manufactured by Dainippon Ink & Chemicals, Product names “Epototo YDCN-701”, “Epototo YDCN-704” manufactured by Toto Kasei Co., Ltd., “Araldite” manufactured by Asahi Kasei Kogyo Co., Ltd. “ECN1235”, “Araldite ECN1273”, “Araldite ECN1299”, “Araldite XPY307”, trade names “EPPN-201”, “EOCN-1025”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd. “RE-306”, trade names “Sumiepoxy ESCN-195X” and “ESCN-220” manufactured by Sumitomo Chemical Co., Ltd., trade name “Epicoat YL-903” manufactured by Japan Epoxy Resin, Dainippon Trade names “Epicron 152” and “Epicron 165” manufactured by Ink Chemical Industries, Ltd., “Epototo YDB-400” and “Epototo YDB-500” manufactured by Tohto Kasei Co., Ltd., and “D. E. R542 ”, trade name“ Araldite 8018 ”manufactured by Asahi Kasei Kogyo Co., Ltd., brominated bisphenol A type epoxy compounds such as“ Sumiepoxy ESB-400 ”and“ Sumiepoxy ESB-700 ”manufactured by Sumitomo Chemical Co., Ltd., manufactured by Nippon Steel Chemical Co., Ltd. Epoxy compounds having a naphthalene skeleton such as “ESN-190”, “ESN-360”, and trade names “HP-4032”, “EXA-4700”, “EXA-4750” manufactured by Dainippon Ink and Chemicals, Inc. Epoxy compounds having a dicyclopentadiene skeleton such as trade names “HP-7200” and “HP-7200H” manufactured by Dainippon Ink & Chemicals, Inc., trade names “YL-933” manufactured by Japan Epoxy Resin, Nippon Kayaku Trishydroxyphenylmethane type epoxy such as “EPPN-501” and “EPPN-502” Compound, product name “TEPIC” manufactured by Nissan Chemical Co., Ltd., heterocyclic epoxy compound such as product name “TGI” manufactured by Mitsubishi Gas Chemical Company, product name “Epicoat 604” manufactured by Japan Epoxy Resin Co., Ltd. Glycidylamine-type epoxy compounds such as “Epototo YH-434”, Asahi Kasei Kogyo Co., Ltd. “Araldite MY720”, Sumitomo Chemical Co., Ltd. “Sumiepoxy ELM-120”, Daicel Chemical Industries, Ltd. Examples include alicyclic epoxy compounds such as the name “Celoxide 2011”, trade names “Araldite CY175”, “Araldite CY179” manufactured by Asahi Kasei Kogyo Co., Ltd., and the product name “HBE-100” manufactured by Shin Nippon Chemical Co., Ltd. It is not limited to. These epoxy compounds can be used alone or in combination of two or more.

  Examples of phenols having two active hydrogens that modify an epoxy compound having two epoxy groups in one molecule include bisphenol A, bisphenol F, and naphthalene diol. Dicarboxylic acids include isophthalic acid and terephthalic acid. Acid, dimer acid, naphthalene dicarboxylic acid, etc., and unsaturated group-containing dicarboxylic acids include reaction products of trimellitic anhydride and unsaturated group-containing monoalcohol, reaction of pyromellitic anhydride and unsaturated group-containing monoalcohol Such as things. The unsaturated group-containing monoalcohol is a hydroxyl group-containing (meth) acrylic acid ester, and includes 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. , Trimethylolpropane di (meth) acrylate, pentaerythritol (tri) acrylate, dipentaerythritol penta (meth) acrylate, and the like.

  The (meth) acrylic anhydride (b) used when synthesizing the polyfunctional epoxy (meth) acrylate compound (A) refers to acrylic anhydride, methacrylic anhydride, and acrylic acid / methacrylic anhydride. It can be used alone or in combination of two.

  The unsaturated group-containing monocarboxylic acid (c) used when synthesizing the epoxy (meth) acrylate compound (A) is a monocarboxylic acid exhibiting radical polymerizability, such as acrylic acid, methacrylic acid, dibasic acid. Examples include an adduct of an acid anhydride and a hydroxyl group-containing (meth) acrylic acid ester, an adduct of a (meth) acrylic acid caprolactone adduct and a dibasic acid anhydride. Examples of the dibasic acid anhydride include succinic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. Examples of the hydroxyl group-containing (meth) acrylic acid ester include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol ( And tri) acrylate and dipentaerythritol penta (meth) acrylate. Particularly preferred here are acrylic acid and methacrylic acid. These unsaturated group-containing monocarboxylic acids (c) can be used alone or in combination of two or more.

  The synthesis blend of the polyfunctional epoxy (meth) acrylate compound (A) is (meth) acrylic anhydride (b) and 1 equivalent of epoxy group of two or more epoxy compounds (a) in one molecule. The total of the carboxyl groups of the unsaturated group-containing monocarboxylic acid (c) is in the range of 0.8 to 1.5 equivalents, preferably in the range of 1.0 to 1.2 equivalents, more preferably 1.0 to 1. It is blended in the range of 05 equivalents. If the total number of carboxyl groups is less than 0.8 equivalent, gelation may occur during the reaction. On the other hand, when it exceeds 1.5 equivalents, unreacted (meth) acrylic anhydride (b) or unsaturated group-containing monocarboxylic acid (c) may remain in the epoxy (meth) acrylate compound.

  In the polyfunctional epoxy (meth) acrylate compound (A), an epoxy compound (a) having two or more epoxy groups in one molecule, a (meth) acrylic anhydride (b), and an unsaturated group-containing monocarboxylic acid ( In the reaction with c), a known polymerization inhibitor described later is further added in the above-mentioned formulation, and the reaction temperature is 60 to 150 ° C., preferably 80 to 130 ° C. in the presence or absence of a diluent described later. The reaction time is preferably in the range of 0.5 to 30 hours in the presence of air. When the reaction temperature is lower than 60 ° C, the reaction is required for a long time, which is uneconomical. On the other hand, when the reaction temperature is higher than 150 ° C, gelation may occur during the reaction. The reaction mixture proceeds with the reaction between the epoxy group and the carboxyl group, and the reaction mixture is reacted to an acid value of less than 10 mgKOH / g, preferably 5 mgKOH / g, more preferably 1 mgKOH / g or less, and the (meth) acrylic anhydride is reacted. It is preferable to reduce the number of carboxyl groups derived from the product (b) and the unsaturated group-containing monocarboxylic acid (c) as much as possible. When the acid value is larger than 10 mgKOH / g, the stability and developability of the ink may be deteriorated.

  Compound (a) having at least two epoxy groups in one molecule in the production of the polyfunctional epoxy (meth) acrylate compound (A), (meth) acrylic anhydride (b), and unsaturated group-containing mono In the carboxylic acid (c) reaction, it is preferable to use a known catalyst in order to facilitate the reaction. Examples of such catalysts include tertiary amines such as triethylamine and dimethylbenzylamine or quaternary ammonium salts, imidazole derivatives such as imidazole and 2-methylimidazole, organic phosphorus compounds such as triphenylphosphine, and triphenylantimony. Mention may be made of organic antimony compounds.

  These catalysts are used in a total of 100 parts by weight of the compound (a) having at least two epoxy groups in one molecule, the (meth) acrylic anhydride (b) and the unsaturated group-containing monocarboxylic acid (c). On the other hand, it can be used in the range of 0.01 to 10 parts by weight, preferably in the range of 0.05 to 5 parts by weight. If it is less than 0.01, it takes a long time for the reaction, which is uneconomical, while if it exceeds 10 parts by weight, the reaction is too early, so that temperature control is difficult, and if the heat generation is high, gelation may occur. There is.

  Compound (a) having at least two epoxy groups in one molecule, (meth) acrylic anhydride (b) and unsaturated group-containing monocarboxylic acid in the production of the polyfunctional epoxy (meth) acrylate compound (A) In the acid (c) reaction, a known polymerization inhibitor may be used in order to ensure stability during production and storage stability of the reaction product.

  Examples of such a polymerization inhibitor include hydroquinone, monomethyl ether hydroquinone, toluhydroquinone, di-tert-4-methylphenol, trimonomethyl ether hydroquinone, phenothiazine, and tert-butylcatechol. The amount used is a total of 100 weights of the compound (a) having at least two epoxy groups in one molecule, the (meth) acrylic anhydride (b) and the unsaturated group-containing monocarboxylic acid (c). Each part can be used in the range of 0.0001 to 1 part by weight, preferably 0.001 to 0.2 part by weight. When the amount is less than 0.0001 part by weight, the polymerization inhibition effect is small, gelation occurs during the reaction, and the target compound may not be obtained, or the storage stability of the reaction product may be significantly reduced. On the other hand, when the amount exceeds 1 part by weight, the curing reaction of the curable resin composition containing the polyfunctional epoxy (meth) acrylate compound (A) and the epoxy compound (B) is inhibited, and the curing contains an uncured product. Products may be obtained and the required performance of each characteristic may not be satisfied.

  The polyfunctional epoxy (meth) acrylate compound (A) of the present invention includes the compound (a) having at least two epoxy groups in one molecule, the (meth) acrylic anhydride (b), and the unsaturated group. A polycarboxylic acid in which a secondary alcoholic hydroxyl group remaining in the reaction product obtained by the reaction of the containing monocarboxylic acid (c) is further reacted with a polybasic acid anhydride (d) to introduce a carboxyl group into the molecule. It is an acid epoxy (meth) acrylate compound.

  Examples of the polybasic acid anhydride (d) include maleic anhydride, succinic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. , Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, dibasic acid anhydrides such as tetrabromophthalic anhydride, and tribasic acid anhydrides such as trimellitic anhydride , Pyromellitic anhydride, biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, ethylene glycol -Bis (anhydrous Trimellitic acid) ester, glycerol alpha, alpha-bis (trimellitic anhydride) ester β- monoacetate, tetracarboxylic acid anhydrides such as naphthalene tetracarboxylic acid dianhydride.

  Of these, polybasic bases having aliphatic or alicyclic structures such as succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. due to ink stability and developability It is preferred to select an acid anhydride. Moreover, the said polybasic acid anhydride (d) can be used individually or in combination of 2 or more types.

  In a preferred embodiment of the present invention, the acid value of the polyfunctional epoxy (meth) acrylate compound (A) may be in the range of 60 to 110 mgKOH / g. The amount of polybasic acid anhydride (d) used depends on the blending ratio of the above (a), (b) and (c), the secondary alcoholic hydroxyl group content in these reaction products, the desired acid value, etc. An amount sufficient to satisfy the above acid value is appropriately used. Further, it is desirable from the viewpoint of ink stability and developability that 95% or more of the acid value is a carboxyl group derived from the polybasic acid anhydride (d). Further, when the acid value is less than 60 mgKOH / g, the solubility in an alkaline aqueous solution is deteriorated, and there is a possibility that development of the formed cured film may be difficult, and solder heat resistance, PCT resistance, etc. may be lowered. is there. On the other hand, if it exceeds 110 mgKOH / g, the surface of the exposed portion may be developed regardless of the exposure conditions in photocuring (temporary curing), and the moisture resistance may be lowered.

  Reaction product obtained by reaction of compound (a) having at least two epoxy groups in one molecule of the present invention, (meth) acrylic anhydride (b) and unsaturated group-containing monocarboxylic acid (c) The reaction between the secondary alcoholic hydroxyl group remaining in the polybasic acid anhydride (d) is carried out at a reaction temperature of 30 to 150 ° C., preferably 70 to 130 ° C. in the presence or absence of a diluent described later. The reaction time can be 0.5 to 30 hours by heating, preferably in the presence of air. When the reaction temperature is lower than 30 ° C., the reaction takes a long time and is uneconomical, whereas when it is higher than 150 ° C., gelation may occur during the reaction. Further, in the reaction, the above-mentioned known polymerization inhibitors and catalysts can be additionally used for the purpose of smoothly promoting the reaction and ensuring the stability during production and the storage stability of the reaction product. .

  Next, the polyfunctional epoxy (meth) acrylate compound (A) of the present invention, an epoxy compound (B) having two or more epoxy groups in one molecule, a photopolymerization initiator (C), and a diluent (D) The photosensitive thermosetting resin composition containing the bismuth will be described.

  About the polyfunctional epoxy (meth) acrylate compound (A), the description of the polyfunctional epoxy (meth) acrylate compound (A) of the present invention described above can be referred to.

  The epoxy compound (B) having two or more epoxy groups in one molecule constituting the photosensitive thermosetting resin composition is not particularly limited, but phenols having two or more active hydrogens in one molecule. Carboxylic acids, glycols, or amines can be obtained by epoxidizing with epichlorohydrin by a known method, alone or in combination of two or more. Also, phenols, carboxylic acids, glycols, or amines having two active hydrogens in one molecule are epoxidized with epichlorohydrin by a known method, alone or in combination of two or more, and further in the molecule An epoxy compound having three or more epoxy groups in one molecule obtained by epoxidizing a secondary alcoholic hydroxyl group with epichlorohydrin by a known method can also be used. Furthermore, it is obtained by epoxidizing phenol novolaks having 3 or more phenolic hydroxyl groups in one molecule obtained by addition condensation of phenols such as phenol and cresol with formaldehyde by a known method. Epoxy compounds having 3 or more epoxy groups in one molecule can also be used.

  A general commercial item can also be used for the epoxy compound (B) which has a 2 or more epoxy group in the said 1 molecule. Examples of commercially available products include “Epicoat 828”, “Epicoat 834”, “Epicoat 1001” and “Epicoat 1004” manufactured by Japan Epoxy Resin Co., Ltd., and “Epicron 840” manufactured by Dainippon Ink & Chemicals, Inc. “Epicron 850”, “Epicron 1050”, “Epicron 2055”, trade names “Epototo 128” manufactured by Tohto Kasei Co., Ltd., trade names “D.E.R. 317”, “D.E.R. .331 ”,“ D.E.R.661 ”,“ D.E.R.664 ”, trade names“ Araldite 250 ”,“ Araldite 260 ”,“ Araldite 2600 ”manufactured by Asahi Kasei Kogyo Co., Ltd., Sumitomo Chemical Co., Ltd. Bisphenols such as “Sumiepoxy ESA-011”, “Sumiepoxy ESA-014”, “Sumiepoxy ELA-128” Type A epoxy compound, trade name “Epicron 830S” manufactured by Dainippon Ink & Chemicals, Inc., product name “Epicoat 807” manufactured by Japan Epoxy Resin Co., Ltd., trade names “Epototo YDF-170”, “Epototo YDF-” manufactured by Tohto Kasei Co., Ltd. 175 ”,“ Epototo YDF-2004 ”,“ Araldite XPY306 ”manufactured by Asahi Kasei Kogyo Co., Ltd., Nippon Kayaku product name“ EBPS-200 ”, Asahi Denka Kogyo product name“ EPX ” -30 ", bisphenol S-type epoxy compounds such as Dainippon Ink & Chemicals' brand name" Epicron EXA1514 ", bisphenol fluorene-type epoxy compounds such as Osaka Gas's brand name" BPFG ", Japan Epoxy Resin Product names “YL-6056”, “YL-6021”, “YX-4” 00 ”,“ YX-4000H ”and other bixylenol type or biphenyl type epoxy compounds, or mixtures thereof, trade names“ Epototo ST-2004 ”,“ ST-2007 ”,“ ST-3000 ”manufactured by Tohto Kasei Co., Ltd. Hydrogenated bisphenol A type epoxy compounds such as “Epicoat 152” and “Epicoat 154” manufactured by Japan Epoxy Resin Co., Ltd., and “D.E.N. 431” and “D.E. N.438 ”, trade names“ Epicron N-690 ”,“ Epicron N-695 ”,“ Epicron N-730 ”,“ Epicron N-770 ”,“ Epicron N-865 ”, manufactured by Dainippon Ink & Chemicals, Product names “Epototo YDCN-701”, “Epototo YDCN-704” manufactured by Toto Kasei Co., Ltd., “Araldite” manufactured by Asahi Kasei Kogyo Co., Ltd. “ECN1235”, “Araldite ECN1273”, “Araldite ECN1299”, “Araldite XPY307”, trade names “EPPN-201”, “EOCN-1025”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd. “RE-306”, trade names “Sumiepoxy ESCN-195X” and “ESCN-220” manufactured by Sumitomo Chemical Co., Ltd., trade name “Epicoat YL-903” manufactured by Japan Epoxy Resin, Dainippon Trade names “Epicron 152” and “Epicron 165” manufactured by Ink Chemical Industries, Ltd., “Epototo YDB-400” and “Epototo YDB-500” manufactured by Tohto Kasei Co., Ltd., and “D. E. R542 ”, trade name“ Araldite 8018 ”manufactured by Asahi Kasei Kogyo Co., Ltd., brominated bisphenol A type epoxy compounds such as“ Sumiepoxy ESB-400 ”and“ Sumiepoxy ESB-700 ”manufactured by Sumitomo Chemical Co., Ltd., manufactured by Nippon Steel Chemical Co., Ltd. Epoxy compounds having a naphthalene skeleton such as “ESN-190”, “ESN-360”, and trade names “HP-4032”, “EXA-4700”, “EXA-4750” manufactured by Dainippon Ink and Chemicals, Inc. Epoxy compounds having a dicyclopentadiene skeleton such as trade names “HP-7200” and “HP-7200H” manufactured by Dainippon Ink & Chemicals, Inc., trade names “YL-933” manufactured by Japan Epoxy Resin, Nippon Kayaku Trishydroxyphenylmethane type epoxy such as “EPPN-501” and “EPPN-502” Compound, product name “TEPIC” manufactured by Nissan Chemical Co., Ltd., heterocyclic epoxy compound such as product name “TGI” manufactured by Mitsubishi Gas Chemical Company, product name “Epicoat 604” manufactured by Japan Epoxy Resin Co., Ltd. Glycidylamine-type epoxy compounds such as “Epototo YH-434”, Asahi Kasei Kogyo Co., Ltd. “Araldite MY720”, Sumitomo Chemical Co., Ltd. “Sumiepoxy ELM-120”, Daicel Chemical Industries, Ltd. Examples include alicyclic epoxy compounds such as the name “Celoxide 2011”, trade names “Araldite CY175”, “Araldite CY179” manufactured by Asahi Kasei Kogyo Co., Ltd., and the product name “HBE-100” manufactured by Shin Nippon Chemical Co., Ltd. It is not limited to. These epoxy compounds can be used alone or in combination of two or more.

  The epoxy compound (B) having two or more epoxy groups in one molecule is formed with a carboxyl group of the polyfunctional epoxy (meth) acrylate compound (A) by performing finish curing with heat after forming a resist pattern. It reacts with each other to form a strong bond, and improves the properties such as adhesion between the cured film of the solder resist and the base material, and heat resistance. The compounding amount is 0.1 to 1.5 equivalents, preferably 0.5 to 1.3 equivalents of the epoxy group with respect to 1 equivalent of the carboxyl group in the molecule of the polyfunctional epoxy (meth) acrylate compound (A). It mix | blends within the range. If the amount is less than 0.1 equivalent, the hygroscopicity of the cured film is increased and the electrical insulation property may be lowered. On the other hand, when it exceeds 1.5 equivalents, photocurability (temporary curing) and alkali developability may be lowered, and image formation of a resist pattern may be difficult.

  Next, the photopolymerization initiator (C) in the curable resin composition of the present invention will be described in detail. The photopolymerization initiator (C) used in the present invention has a function of generating radicals by irradiation with ultraviolet rays (light) and curing by radical polymerization when the curable resin composition is photocured (temporarily cured).

  As such a photopolymerization initiator (C), known ones can be used. Preferred photopolymerization initiators (E) include, for example, benzoins such as benzoin, benzyl, benzoin methyl ether, and benzoin isopropyl ether. And benzoin alkyl ethers, acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2- Atophenones such as morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2- Ethyl anthraquinone, 2-amino Anthraquinones such as anthraquinone, thioxanthones such as 2,4-dimethylthioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylamino Examples include benzophenones such as benzophenone and xanthones, and these can be used alone or in combination of two or more. Further, such a photopolymerization initiator (C) is a benzoic acid ester such as ethyl-4-dimethylaminobenzoate or 2- (dimethylamino) ethylbenzoate, or a tertiary amine such as triethylamine or triethanolamine. Such known photosensitizers can be used alone or in combination of two or more.

  The photopolymerization initiator (C) is preferably used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the polyfunctional epoxy (meth) acrylate compound (A). It is preferably used in the range of ˜20 parts by weight. When the amount is less than 0.1 parts by weight, the polymerization does not proceed due to ultraviolet (light) irradiation, and the formed film may be uncured and the alkali developability may be deteriorated. This is because the heat resistance and mechanical properties of the film may be reduced.

  Next, the diluent (D) in the curable resin composition of the present invention will be described in detail. Examples of the diluent (D) used in the curable resin composition of the present invention include an organic solvent and a (meth) acrylic ester, dissolve the polyfunctional epoxy (meth) acrylate compound (A), and a solder resist ink. As a result, a diluent with reactivity such as (meth) acrylic acid ester is incorporated into the network during radical polymerization, improving photocurability, heat resistance, and crack resistance. There is an effect of improving the adhesion to the substrate.

  In addition, the diluent (D) includes a compound (a) having at least two epoxy groups in one molecule and (meth) acrylic anhydride (in the production of the polyfunctional epoxy (meth) acrylate compound (A). Purpose of obtaining a stable reaction product which does not cause gelation in the reaction of b) and an unsaturated group-containing monocarboxylic acid (c), and further in the reaction of this reaction product with a polybasic acid anhydride (d). And can be adjusted to an appropriate viscosity with the diluent (D).

  Examples of such diluent (D) include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, and propylene. Glycol ethers such as glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, ethanol, propanol, ethylene glycol, propylene glycol, etc. Of organic solvents such as alcohols, aliphatic hydrocarbons such as octane and decane, petroleum ethers such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. It can be exemplified, but the invention is not limited thereto. These can be used alone or in combination of two or more.

  In addition, the diluent (D) can be used by replacing part or all of the organic solvent with (meth) acrylic acid esters having photocurability. Examples of such (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl. (Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, alkyl (meth) acrylate such as stearyl (meth) acrylate, epoxy group-containing (meth) acrylate such as glycidyl (meth) acrylate, ( Aminoalkyl (meth) acrylates such as (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropy Hydroxyalkyl (meth) acrylates such as (meth) acrylate, mono- or di (meth) acrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, N, N-dimethyl (meth) acrylamides, N, N -Aminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, polyhydric alcohols such as tris-hydroxyethylisosinurate, or , These ethylene oxide or propylene oxide adduct polyvalent (meth) acrylates, phenoxyethyl (meth) acrylate, bisphenol A polyethoxydi ( ) (Meth) acrylates of ethylene oxide or propylene oxide adducts of phenols such as acrylate, glycidyl ether (meth) acrylates such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, ε -Ε-caprolactone-modified (meth) acrylates such as caprolactone-modified tris (acryloxyethyl) isocyanurate, melamine (meth) acrylate, and the like can be mentioned, but are not limited thereto. These can be used alone or in combination of two or more.

  The usage-amount of the said diluent (D) can be mix | blended in the range of 1-300 weight part with respect to 100 weight part of polyfunctional epoxy (meth) acrylate compounds (A). Moreover, when using (meth) acrylic acid ester as said diluent (D), the usage-amount is 3-50 with respect to 100 weight part of said acid-modified epoxy (meth) acrylate compounds (A). It is preferable to use in the range of parts by weight, preferably in the range of 5 to 15 parts by weight. If the amount is less than 3 parts by weight, the effect of imparting photocurability may not be sufficient, and if it exceeds 50 parts by weight, the dryness to touch of the dry film may be lowered.

  The curable resin composition of the present invention includes a carboxyl group in the molecule of the polyfunctional epoxy (meth) acrylate compound (A) in the thermosetting step (finish curing) and two or more in one molecule as necessary. For the purpose of accelerating the reaction with the epoxy compound (B) having an epoxy group, a curing accelerator can be added. Examples of the curing accelerator include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazole derivatives such as (2-cyanoethyl) -2-ethyl-4-methylimidazole, guanamines such as guanamine, acetoguanamine, benzoguanamine, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine And amine compounds such as 4-methyl-N, N-dimethylbenzylamine and melamine. These can be used alone or in combination of two or more.

  The amount of the curing accelerator used is in the range of 0.1 to 10 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the polyfunctional epoxy (meth) acrylate compound (A). Can be used in a range of When the amount is less than 0.1 parts by weight, the effect of accelerating the curing reaction of the epoxy compound (B) having two or more epoxy groups in one molecule is reduced. There exists a possibility that the life of a resin composition may become short.

  An inorganic filler can be added to the curable resin composition of the present invention for the purpose of improving the adhesion to the printed wiring board, if necessary. For example, inorganic fillers such as talc, silica, barium sulfate, barium titanate, silicon oxide, aluminum oxide, calcium carbonate, and aluminum hydroxide can be blended. These inorganic fillers can be added in a range of up to 150 parts by weight with respect to 100 parts by weight of the curable resin composition. If it exceeds 150 parts by weight, the curability may be adversely affected and the physical properties of the cured film may be reduced.

  In addition to the above components, the curable resin composition of the present invention may contain various colorants, leveling agents, antifoaming agents, and the like that are added to ordinary solder resist resin compositions as necessary. it can.

  The curable resin composition of the present invention is obtained by uniformly mixing the above-described blending components (A), (B), (C) and (D), and blending components added as necessary, using a roll mill, a sand mill or the like. Can be obtained by mixing. Moreover, application | coating on the printed wiring board of the curable resin composition of this invention is normally performed by the screen printing method, the electrostatic coating method, the roll coater method, the curtain coater method, etc. After coating, dry at 60 to 90 ° C for 10 to 60 minutes, irradiate with active energy rays such as ultraviolet rays, and then remove unexposed parts with dilute alkaline aqueous solution such as 0.1 to 5 wt% sodium carbonate aqueous solution Then, a solder pattern image is formed by development. After that, in order to completely cure the film, heat treatment (100 to 180 ° C. for 5 to 60 minutes) as a final curing using a hot air dryer or far infrared rays or the like results in two or more epoxy groups in one molecule. When (meth) acrylic acid esters are used as the acid-modified epoxy (meth) acrylate compound (A) and the diluent (D) in addition to the curing reaction of the epoxy compound (B) having (meth) acrylic acid esters Polymerization is promoted, and a cured film having excellent adhesion, heat resistance, and mechanical properties can be obtained. Furthermore, if necessary, for example, by heating to a temperature of 140 to 180 ° C. and thermosetting, further, a polyfunctional epoxy (meth) acrylate compound (A) and a diluent (D) (meth) acrylic For the purpose of accelerating the polymerization of acid esters, it is possible to obtain a cured film having excellent characteristics by exposing it again to ultraviolet rays (light).

  As an irradiation light source for ultraviolet (light) curing, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used.

  The polyfunctional epoxy (meth) acrylate compound of the present invention and the photosensitive thermosetting resin composition containing the polyfunctional epoxy (meth) acrylate compound thus obtained are used for the production of printed wiring boards, particularly solder resists. Liquid solder resist ink and dry film resist electronic materials used in the manufacture of IC packages such as BGA (ball grid array) and CSP (chip scale package) using printed wiring board and sealing resin In the field, dryness to the touch, sensitivity, alkali developability, development life, cold heat, without causing cracks or peeling in the cured film formed in the PCT test (pressure cooker test), which is a long-term reliability test during mounting. Cycle test, solder heat resistance, adhesion to substrate, plating property, electrical An advantageous effect that is suitable for excellent film forming the insulation.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

  In this embodiment, “parts” means parts by weight unless otherwise specified. In this example, the polyfunctional epoxy (meth) acrylate resin means that the polyfunctional epoxy (meth) acrylate compound is diluted with an organic solvent and / or a diluent of (meth) acrylic acid esters. To do.

<Synthesis example of polyfunctional epoxy acrylate resin>
Synthesis example 1
<Reaction pathway>
<Reaction 1-1)>
By reacting trimellitic anhydride with 2-hydroxyethyl acrylate, a 2-hydroxyethyl acrylate / trimellitic anhydride adduct (dicarboxylic acid compound) is produced.

([Chemical Formula 7]: trimellitic anhydride + 2-hydroxyethyl acrylate
→ Dicarboxylic acid compound [Intermediate 1-1])

<Reaction 1-2)>
Next, when a bisphenol A type epoxy compound, acrylic acid, and methacrylic anhydride are charged and reacted, the following two reactions (reaction 1-2-1, reaction 1-2-2) occur simultaneously.

First, the first reaction 1-2-1 of the two reactions that occur simultaneously will be described.
In the first reaction 1-2-1, the dicarboxylic acid compound [intermediate 1-1] produced in the above reaction 1-1 is reacted with a bisphenol A type epoxy compound as an intermediate [intermediate 1-2-1a ] Is generated.

([Chemical Formula 8]: bisphenol A type epoxy compound + dicarboxylic acid compound [intermediate 1-1] → [intermediate 1-2-1a])

  Here, M1 of [Intermediate 1-2-1a] is a hydrogen atom (-H).

Thereafter, a part of the epoxy group at the molecular end of [Intermediate 1-2-1a] reacts with acrylic acid (Reaction [Chemical 9]), and [Intermediate 1-2-1b, Intermediate 1-2- 1b '] is generated.

  [Intermediate 1-2-1b, Intermediate 1-2-1b ′] has two types of cases where acrylic acid reacts at the left end and acrylic acid reacts at the right end as in the molecular formula above. There is. Here, Q1 is a residue of acrylic acid, and M1 is a hydrogen atom.

  Subsequently, the reaction of these two [intermediate 1-2-1b, intermediate 1-2-1b '] and methacrylic anhydride occurs (reaction [Chem. 12]).

が付加されると同時に、メタクリル酸

を遊離する。この遊離したメタクリル酸は[中間物1-2-1b、中間物1-2-1b’]の残りのエポキシ基と反応し、分子末端がQ（Qはアクリル酸の残基、またはメタクリル酸の残基）となり、[中間物1-2-1c]を生成する（反応[化１２]）。

Methacrylic anhydride reacts at the position of -OM1 (M1: -H) of [Intermediate 1-2-1b, Intermediate 1-2-1b ']

As methacrylic acid is added

Is released. This liberated methacrylic acid reacts with the remaining epoxy groups of [Intermediate 1-2-1b, Intermediate 1-2-1b '], and the molecular end is Q (Q is the residue of acrylic acid or methacrylic acid Residue) to produce [Intermediate 1-2-1c] (reaction [Chemical 12]).

  Here, (Reaction [Chemical 9]) and (Reaction [Chemical 12]) are reversed in the order of reaction, that is, after [Intermediate 1-2-1a] is produced, this [Intermediate 1-2- 1a] and methacrylic anhydride react first (reaction [Chemical 12]), and then acrylic acid reacts (Reaction [Chemical 9]). 1-2-1c] will be the same.

Next, reaction 1-2-2 which is the second reaction will be described as follows.
The second reaction 1-2-2 is the reaction of the bisphenol A type epoxy compound and acrylic acid charged in the above reaction 1-2) (reaction [Chemical 13) and [intermediate 1-2-2a] can get. Next, methacrylic anhydride reacts (reaction [Chem. 14]) to produce [Intermediate 1-2-2b]. Specifically, first, one of the terminal epoxy groups of the bisphenol A type epoxy compound and acrylic acid react to form [Intermediate 1-2-2a], and at the same time, a hydroxyl group (-OM1, M1:- H) occurs (reaction [Chemical 13]). Next, methacrylic anhydride is reacted with this hydroxyl group to add a methacrylic group, and at the same time methacrylic acid is liberated. This methacrylic acid reacts with the remaining epoxy group of [intermediate 1-2-2a], and [intermediate Product 1-2-2b] (reaction [Chem. 14]).

  That is, in the reaction 1-2, [Intermediate 1-2-1c] and [Intermediate 1-2-2b] are produced and mixed.

Thereafter, tetrahydrophthalic anhydride is charged into the mixture of [Intermediate 1-2-1c] and [Intermediate 1-2-2b] and reacted. This tetrahydrophthalic anhydride is one of the hydroxyl groups (—OH) when M2 is a hydrogen atom (—H) at the position of —OM2 of [Intermediate 1-2-1c] and [Intermediate 1-2-2b]. (Reaction 1-3-1 [Chemical 15], Reaction 1-3-2 [Chemical 16]) as products, [Product 1-3-1] and [Product 1-3, respectively] -2] is generated.
(Reaction 1-3-1)

This [Product 1-3-1] corresponds to [Chemical Formula 3] in the present specification, wherein X is a residue of bisphenol A and Y is a dicarboxylic acid (2-hydroxyethyl methacrylate and anhydrous trihydrate). It corresponds to the residue of an adduct of merit acid).
(Reaction 1-3-2)

This [Product 1-3-2] corresponds to m = 0 of [Chemical Formula 1] in this specification (that is, when n = 0 of [Chemical Formula 3] of the specification), X in [Chemical Formula 3] corresponds to the residue of bisphenol A (if m = 0 or n = 0, Y does not exist).
As described above, in Synthesis Example 1, an example in which [Chemical Formula 1] and [Chemical Formula 3] (m = 0 or n = 0) are synthesized simultaneously has been shown.

  Specifically, the synthesis was performed as follows.

Charge 74.2 parts of trimellitic anhydride and 54.6 parts of 2-hydroxyethyl acrylate to a reaction vessel equipped with a gas introduction tube, a stirring device, a cooling tube, and a thermometer, and heat with stirring while blowing air. The temperature was kept at 85 to 95 ° C. for reaction. The reaction was followed by IR and continued until the absorption of unreacted trimellitic anhydride (1780 cm ⁻¹ ) disappeared. The reaction took 4 hours. Next, bisphenol A type epoxy compound (trade name “AER260” manufactured by Asahi Kasei Kogyo Co., Ltd.) 275.6 parts, acrylic acid 26.4 parts, methacrylic anhydride 55.4 parts, triphenylphosphine 1.4 parts, monomethyl ether 0.6 part of hydroquinone was added and heated under stirring to react for 10 hours while maintaining the temperature at 110 to 120 ° C. to obtain a reaction product having an acid value of 4 mgKOH / g. Thereafter, 161.5 parts of tetrahydrophthalic anhydride was added, and the mixture was further reacted for 5 hours while maintaining the temperature at 100 to 110 ° C. with stirring to obtain a polyfunctional epoxy acrylate compound having an acid value of 95 mgKOH / g. 96.8% of this acid value is derived from the carboxyl group produced by the reaction of tetrahydrophthalic anhydride. This polyfunctional epoxy acrylate compound was diluted with 433.1 parts of carbitol acetate to obtain a polyfunctional epoxy acrylate resin (a-1) having a nonvolatile content of 60%. FIG. 1 shows a nuclear magnetic resonance spectrum of the polyfunctional epoxy acrylate compound obtained in Synthesis Example 1. FIG. 2 shows an infrared absorption spectrum of the polyfunctional epoxy acrylate compound obtained in Synthesis Example 1.

Synthesis example 2
<Reaction pathway>
<Reaction 2-1)>
By reacting pyromellitic anhydride with 2-hydroxyethyl acrylate, a 2-hydroxyethyl acrylate / pyromellitic anhydride adduct (dicarboxylic acid compound) is produced.

([Chemical Formula 17]: pyromellitic anhydride + 2-hydroxyethyl acrylate → dicarboxylic acid compound [intermediate 2-1])

<Reaction 2-2)>
Next, when a bisphenol F type epoxy compound, acrylic acid, and acrylic anhydride are charged and reacted, the following two reactions (reaction 2-2-1 and reaction 2-2-2) occur simultaneously.

First, the first reaction 2-2-1 of the two reactions that occur simultaneously will be described.
In the first reaction 2-2-1, the dicarboxylic acid compound [intermediate 2-1] produced in reaction 2-1 reacts with the bisphenol F-type epoxy compound [intermediate 2-2-1a]. Produces.

Here, M1 of [Intermediate 2-2-1a] is a hydrogen atom (H). Thereafter, a part of the epoxy group at the molecular end of [Intermediate 2-2-1a] reacts with acrylic acid (Reaction [Chemical Formula 19]) to produce [Intermediate 2-2-1b].

  [Intermediate 2-2-1b, Intermediate 2-2-1b ′] has two types of cases where acrylic acid reacts at the left end and acrylic acid reacts at the right end, as in the molecular formula above. is there. Here, Q is a residue of acrylic acid, and M1 is a hydrogen atom.

Next, the reaction of the two [intermediate 2-2-1b, intermediate 2-2-1b ′] and acrylic anhydride occurs (reaction [Chemical Formula 20]). Acrylic acid anhydride reacts at the position of -OM1 (M1: -H) of [Intermediate 2-2-1b, Intermediate 2-2-1b '], and an acrylic group is added at the same time. Is released. This acrylic acid reacts with the remaining epoxy group of [Intermediate 2-2-1b, Intermediate 2-2-1b '], and both ends of the molecule become Q (residue of acrylic acid). 2-2-1c] is generated.

  Here, (reaction [Chem. 19]) and (reaction [Chem. 20]) are reversed in the order of reaction, that is, after [Intermediate 2-2-1a] is produced, 1a] and acrylic acid anhydride react first (reaction [Chemical Formula 20]), and acrylic acid reacts later (Reaction [Chemical Formula 19]). However, the final product is always [intermediate]. 2-2-1c] will be the same.

（[化２１]：ビスフェノールF型エポキシ化合物+アクリル酸→[中間物2-2-2a]）

Next, reaction 2-2-2, which is the second reaction, will be described.
In the second reaction 2-2-2, the bisphenol F-type epoxy compound charged in the above reaction 2-2) reacts with acrylic acid (reaction [Chemical Formula 21]), and [intermediate 2-2-2a] becomes can get. Next, acrylic anhydride reacts (reaction [Chemical Formula 22]) to produce [Intermediate 2-2-2b]. Specifically, first, one of the terminal epoxy groups of the bisphenol F-type epoxy compound and acrylic acid react with each other to produce [Intermediate 2-2-2a], and at the same time a hydroxyl group (-OM1, M1:- H) occurs (reaction [Chemical Formula 21]). Next, acrylic acid anhydride reacts with this hydroxyl group to add an acrylic group, and at the same time, acrylic acid is released. This acrylic acid reacts with the remaining epoxy group of [intermediate 2-2-2a], and [intermediate 2-2-2b] (reaction [Chemical Formula 22]).

([Chemical Formula 21]: Bisphenol F-type epoxy compound + acrylic acid → [Intermediate 2-2-2a])

（反応2-3-2）

That is, in the reaction 2-2, [intermediate 2-2-1c] and [intermediate 2-2-2b] are produced and mixed. Then, with respect to a part of the hydroxyl group (—OH) when M2 is a hydrogen atom (—H) at the position of −OM2 of [Intermediate 2-2-1c] and [Intermediate 2-2-2b] Reaction (Reaction 2-3-1 [Chemical Formula 23], Reaction 2-3-2 [Chemical Formula 24]), and [Product 2-3-1] and [Product 2-3-2-] are obtained as products, respectively. Generated.
(Reaction 2-3-1)

(Reaction 2-3-2)

（式2-2）

As described above, in Synthesis Example 2, the polyfunctional epoxy (meth) acrylate compound has two structures as shown above. If it repeats, the following two will be obtained.
(Formula 2-1)

(Formula 2-2)

Yは無水ピロメリット酸が2-ヒドロキシエチルメタクリレートと反応して得られるジカルボン酸の残基となる。

Among these structures, (Equation 2-1) [Chemical 25] corresponds to [Chemical 3], and (Equation 2-2) [Chemical 26] corresponds to m = 0 of [Chemical 1]. In addition, a mixture in the range of 0 to 100 is obtained at the same time.
X is the residue of bisphenol F,

Y is a residue of dicarboxylic acid obtained by reacting pyromellitic anhydride with 2-hydroxyethyl methacrylate.

アクリル酸が反応したアクリル酸の残基、及びアクリル酸無水物がMの位置に反応して生成するアクリル酸が反応したアクリル酸の残基となり、いずれもアクリル酸の残基である。 Q is

The residue of acrylic acid reacted with acrylic acid and the residue of acrylic acid reacted with acrylic acid generated by the reaction of acrylic acid anhydride at the M position are both residues of acrylic acid.

水素原子、アクリル酸無水物が反応したカルボン酸残基、テトラヒドロ無水フタル酸が反応した残基となる。 M is

A hydrogen atom, a carboxylic acid residue reacted with acrylic anhydride, and a residue reacted with tetrahydrophthalic anhydride.

  Specifically, the synthesis was performed as follows.

In a reaction vessel similar to that used in Synthesis Example 1, 158.9 parts of pyromellitic anhydride and 202.75 parts of 2-hydroxyethyl acrylate were charged, and heated with stirring while blowing air, so that the temperature was 85 to 95. The reaction was held at 0 ° C. The reaction was followed by IR and continued until the absorption of unreacted trimellitic anhydride (1780 cm ⁻¹ ) disappeared. The reaction took 4 hours. Next, bisphenol F type epoxy compound (trade name “Epicron 830S” manufactured by Dainippon Ink and Chemicals, Inc.) 247.4 parts, acrylic acid 36.0 parts, acrylic acid anhydride 63.0 parts, triphenylphosphine 1.4 Part and 0.6 part of monomethyl ether hydroquinone were heated under stirring and reacted for 10 hours while maintaining the temperature at 110 to 120 ° C. to obtain a reaction product having an acid value of 1 mgKOH / g. Thereafter, 235.2 parts of tetrahydrophthalic anhydride was added, and the mixture was further reacted for 5 hours while maintaining the temperature at 100 to 110 ° C. with stirring to obtain a polyfunctional epoxy acrylate compound having an acid value of 95 mgKOH / g. 99.1% of this acid value is derived from the carboxyl group produced by the reaction of tetrahydrophthalic anhydride. This polyfunctional epoxy acrylate compound was diluted with 628.6 parts of carbitol acetate to obtain a polyfunctional epoxy acrylate resin (a-2) having a nonvolatile content of 60%.

上記分子式のようにQはアクリル酸の残基、M1は水素原子である。 Synthesis example 3
<Reaction pathway>
First, a bisphenol A type epoxy compound, acrylic acid, and acrylic anhydride are charged and reacted. Here, the following three reactions (reaction 3-1, reaction 3-2, reaction 3-3) occur. As shown in [Chemical Formula 1], both X and Y are bisphenol A residues.
(Reaction 3-1)

As in the molecular formula above, Q is a residue of acrylic acid, and M1 is a hydrogen atom.

(Reaction 3-2)
Simultaneously with the above reaction, a reaction between the acrylic anhydride and the hydroxyl group in the epoxy resin occurs (Reaction 3-2). Acrylic anhydride reacts at the position of -OM1 (M1: -H) of the epoxy resin to add acrylic group and release acrylic acid at the same time.

(Reaction 3-3)
Addition of acrylic acid anhydride to [Intermediate 3-1] just produced also occurs.

Acrylic acid liberated in reactions 3-2 and 3-3 reacts with the remaining epoxy groups in [Intermediate 3-1, 3-2, 3-3], and both ends of the molecule are Q (residue of acrylic acid At this stage, [Intermediate 3-4] and [Chemical 34] are produced.
[Intermediate 3-4]

Next, M2 in the intermediate 3-4 [Chemical Formula 34] is reacted with tetrahydrophthalic anhydride in the hydrogen part.

In this structure, (Equation 3-1) corresponds to that of [Chemical Formula 1]. In addition, a mixture in the range of 0 to 100 can be obtained simultaneously. So X and Y are the same bisphenol A residues,

  The acrylic acid residue reacted with acrylic acid and the acrylic acid residue produced by the reaction of acrylic acid generated by the reaction of acrylic acid anhydride at the M position are both acrylic acid residues.

水素原子、アクリル酸無水物が反応したカルボン酸残基、テトラヒドロ無水フタル酸が反応した残基となる。 M is

A hydrogen atom, a carboxylic acid residue reacted with acrylic anhydride, and a residue reacted with tetrahydrophthalic anhydride.

  Specifically, the synthesis was performed as follows.

  A reaction vessel similar to that used in Synthesis Example 1 was charged with 400.0 parts of a bisphenol A type epoxy compound (“jER # 1001” manufactured by Japan Epoxy Resin Co., Ltd.), dissolved, and then stirred with 43.2 parts of acrylic acid. , 176.4 parts of acrylic anhydride, 1.4 parts of triphenylphosphine, and 0.6 parts of monomethyl ether hydroquinone were heated and reacted for 10 hours while maintaining the temperature at 110 to 120 ° C. while blowing air. A reaction product having an acid value of 1 mgKOH / g was obtained. Thereafter, 398.0 parts of tetrahydrophthalic anhydride was added, and the mixture was further reacted for 5 hours while maintaining the temperature at 100 to 110 ° C. with stirring to obtain a polyfunctional epoxy acrylate compound having an acid value of 95 mgKOH / g. 99% of this acid value is derived from the carboxyl group produced by the reaction of tetrahydrophthalic anhydride. This polyfunctional epoxy acrylate compound was diluted with 441.9 parts of carbitol acetate to obtain a polyfunctional epoxy acrylate resin (a-3) having a nonvolatile content of 60%.

Synthesis example 4
<Reaction pathway>
The polyfunctional epoxy (meth) acrylate compound obtained in Synthesis Example 4 is structurally the same as the compound obtained in Synthesis Example 1. The difference is that the amount of tetrahydrophthalic anhydride added at the end of the reaction is less than in Synthesis Example 1 and the final compound has an acid value of 40 mgKOH / g. That is, the proportion of tetrahydrophthalic anhydride residues constituting M in the structure is reduced, and the proportion of hydrogen atoms is increased. Therefore, referring to the above reaction formula, X, Y, Q, M, n, and m are as follows.

  Specifically, the synthesis was performed as follows.

A reaction vessel similar to that used in Synthesis Example 1 was charged with 74.2 parts of trimellitic anhydride and 54.6 parts of 2-hydroxyethyl acrylate, and heated with stirring while blowing air to a temperature of 85 to 95. The reaction was held at 0 ° C. The reaction was followed by IR and continued until the absorption of unreacted trimellitic anhydride (1780 cm ⁻¹ ) disappeared. The reaction took 4 hours. Next, bisphenol A type epoxy compound (trade name “AER260” manufactured by Asahi Kasei Kogyo Co., Ltd.) 275.6 parts, acrylic acid 26.4 parts, methacrylic anhydride 55.4 parts, triphenylphosphine 1.4 parts, monomethyl ether 0.6 part of hydroquinone was added and heated under stirring to react for 10 hours while maintaining the temperature at 110 to 120 ° C. to obtain a reaction product having an acid value of 4 mgKOH / g. Thereafter, 53.2 parts of tetrahydrophthalic anhydride was added, and the mixture was further reacted for 5 hours while maintaining the temperature at 100 to 110 ° C. with stirring to obtain a polyfunctional epoxy acrylate compound having an acid value of 40 mgKOH / g. 90.7% of this acid value is derived from the carboxyl group produced by the reaction of tetrahydrophthalic anhydride. This polyfunctional epoxy acrylate compound was diluted with 360.9 parts of carbitol acetate to obtain a polyfunctional epoxy acrylate resin (a-4) having a nonvolatile content of 60%.

Synthesis example 5
<Reaction pathway>
The polyfunctional epoxy (meth) acrylate compound obtained in Synthesis Example 5 is structurally similar to the compound obtained in Synthesis Example 1 in the same manner as in Synthesis Example 1. The difference is that the blending ratio of acrylic acid and methacrylic anhydride is different between Synthesis Example 1 and Synthesis Example 5, and the blending amount of acrylic acid is large and the blending amount of methacrylic anhydride is small. In other words, the ratio of acrylic acid residues constituting Q in the structure and methacrylic acid residues produced by the reaction of methacrylic acid at the M position differs from the methacrylic acid residues at the Q position. The ratio of the acid residue is large, and instead the ratio of the methacrylic acid residue is small. In addition, Compound 1 has an acid value of 100 mgKOH / g, and Synthesis Example 5 has an acid value of 122 mgKOH / g. That is, the proportion of tetrahydrophthalic anhydride residues constituting M in the structure is increased, and the proportion of hydrogen atoms is decreased instead. Therefore, with reference to the above reaction formula, in Synthesis Example 5, X, Y, Q, M, n, and m are as follows.

  Specifically, the synthesis was performed as follows.

A reaction vessel similar to that used in Synthesis Example 1 was charged with 74.2 parts of trimellitic anhydride and 54.6 parts of 2-hydroxyethyl acrylate, and heated with stirring while blowing air to a temperature of 85 to 95. The reaction was held at 0 ° C. The reaction was followed by IR and continued until the absorption of unreacted trimellitic anhydride (1780 cm ⁻¹ ) disappeared. The reaction took 4 hours. Next, bisphenol A type epoxy compound (trade name “AER260” manufactured by Asahi Kasei Kogyo Co., Ltd.) 275.6 parts, acrylic acid 39.4 parts, methacrylic anhydride 27.7 parts, triphenylphosphine 1.4 parts, monomethyl ether 0.6 part of hydroquinone was added and heated under stirring to react for 10 hours while maintaining the temperature at 110 to 120 ° C. to obtain a reaction product having an acid value of 4 mgKOH / g. Thereafter, 225.0 parts of tetrahydrophthalic anhydride was added, and the mixture was further reacted for 5 hours while maintaining the temperature at 100 to 110 ° C. with stirring to obtain a polyfunctional epoxy acrylate compound having an acid value of 122 mgKOH / g. 97.4% of this acid value is derived from the carboxyl group produced by the reaction of tetrahydrophthalic anhydride. This polyfunctional epoxy acrylate compound was diluted with 465.7 parts of carbitol acetate to obtain a polyfunctional epoxy acrylate resin (a-5) having a nonvolatile content of 60%.

Synthesis Example 6 (for comparison)
In a reaction vessel similar to that used in Synthesis Example 1, 345 parts of a cresol novolac type epoxy compound (trade name “Epiclon N-690” manufactured by Dainippon Ink & Chemicals, Inc.), 117 parts of acrylic acid, triphenylphosphine 4 parts, 0.6 parts of monomethyl ether hydroquinone were charged, and heated with stirring while blowing air. The temperature was maintained at 110 to 120 ° C. and reacted for 10 hours to obtain a reaction product having an acid value of 1 mg KOH / g. . Next, 137 parts of tetrahydrophthalic anhydride was added, the temperature was maintained at 100 to 110 ° C. with stirring, and the mixture was further reacted for 5 hours to obtain a polyfunctional epoxy acrylate compound having an acid value of 85 mgKOH / g. 99.1% of this acid value is derived from the carboxyl group reacted with tetrahydrophthalic anhydride. This polyfunctional epoxy acrylate compound was diluted with 401 parts of carbitol acetate to obtain a polyfunctional epoxy acrylate resin (b-1) having a nonvolatile content of 60%.

Synthesis Example 7 (for comparison)
In a reaction vessel similar to that used in Synthesis Example 1, 500 parts of a bisphenol A type epoxy compound (trade name “jER # 1004” manufactured by Japan Epoxy Resin), 76.7 parts of acrylic acid, 1.2 parts of triphenylphosphine, 0.8 parts of monomethyl ether hydroquinone was charged and heated with stirring while blowing air, and the temperature was maintained at 110 to 120 ° C. and reacted for 10 hours to obtain a reaction product having an acid value of 1 mg KOH / g. Next, 186 parts of tetrahydrophthalic anhydride was added, the temperature was maintained at 100 to 110 ° C. with stirring, and the mixture was further reacted for 5 hours to obtain an epoxy acrylate compound having an acid value of 90 mgKOH / g. 99.3% of this acid value is derived from the carboxyl group produced by the reaction of tetrahydrophthalic anhydride. This epoxy acrylate compound was diluted with 508.3 parts of carbitol acetate to obtain an epoxy acrylate resin (b-2) having a nonvolatile content of 60%.

<Preparation of photosensitive thermosetting resin composition>
Examples 1 to 5 and Comparative Examples 6 and 7
Polyfunctional epoxy (meth) acrylate resin (a-1 to a-3, b) obtained by diluting the multifunctional epoxy (meth) acrylate compound (A) obtained in Synthesis Examples 1 to 7 above in the diluent (D) -1 to b-5) were blended with the compositions shown in Table 1 to prepare photosensitive thermosetting resin compositions.

The epoxy compound (B) having two or more epoxy groups in one molecule in the curable resin composition is a bisphenol A type epoxy compound (trade name “Araldite 260” manufactured by Asahi Kasei Kogyo Co., Ltd.), photopolymerization start As the agent (C), trade name “Irgacure 907” manufactured by Ciba Specialty Chemicals was used. In addition, as a defoaming agent, “BYK-A555”, a trade name of Big Chemie Japan, and a trade name “Phthalocyanine Green”, manufactured by Dainichi Seika Kogyo Co., Ltd., were used as a pigment.

  Table 1 shows the composition of the photosensitive thermosetting resin composition and the results of the evaluation described below.

<Evaluation Item> The evaluation items are items shown in the following (1) to (9).
(1) Dryness to touch The photosensitive thermosetting resin composition shown in Table 1 was applied on the entire surface of the substrate with copper foil by screen printing, and dried in a hot air drying oven at 80 ° C. for 30 minutes. Thereafter, the substrate was taken out from the drying furnace, allowed to cool to room temperature, and the touch drying property of the coating film was examined. Judgment criteria are as follows.
○: No tack, △: No tack, but thin fingerprint, x: There is tack

(2) Alkali developability The resin composition described in Table 1 was applied on the entire surface of the substrate with copper foil by screen printing, and dried in a hot air drying oven at 80 ° C. for 20, 40, 60 minutes. Thereafter, the substrate is taken out from the drying furnace, allowed to cool to room temperature, developed with a 1% by weight sodium carbonate aqueous solution at 30 ° C. for 60 seconds under the condition of a spray pressure of 0.2 MPa, and the presence or absence of development residue of the dry coating film is visually observed. confirmed. Judgment criteria are as follows.
○: Completely developed, Δ: Part of the coating film remains, ×: The coating film remains completely

(3) Sensitivity The resin composition described in Table 1 was applied on the entire surface of the substrate with copper foil by screen printing, and dried in a hot air drying oven at 80 ° C. for 30 minutes. Thereafter, the substrate is taken out from the drying furnace, allowed to cool to room temperature, and a step tablet (Kodak No. 2, total 21 steps) is placed on the coating film, and a metal halide lamp (350 nm) is used as a light source under reduced pressure, and an integrated UV light amount of 600 mJ. After exposure under the conditions of / cm ² and removing the step tablet, development is performed with a 1% by weight sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 60 seconds, and the number of steps of the remaining coating film is visually counted. Was used to evaluate the sensitivity to ultraviolet rays. A larger number of steps means higher sensitivity to ultraviolet rays.

(4) Adhesiveness The resin composition described in Table 1 was applied on the entire surface of the substrate with copper foil by screen printing, and dried in a hot air drying oven at 80 ° C. for 30 minutes. Thereafter, the substrate is taken out from the drying furnace, allowed to cool to room temperature, exposed under reduced pressure using a metal halide lamp (350 nm) as a light source under conditions of an integrated UV light quantity of 600 mJ / cm ² , and further heated in a hot air drying furnace at 150 ° C. Heat cured for minutes. Thereafter, the substrate was taken out from the drying furnace and allowed to cool to room temperature. The adhesion of the obtained cured coating film is determined according to JIS.
Evaluation was made according to D0202. Judgment criteria are as follows.
○: The number of grids remaining completely 100, △: The number of grids remaining less than 100 and 60 or more, ×: The number of grids remaining less than 60

(5) Solder heat resistance Each board | substrate was produced on the same conditions as evaluation item (4). The obtained cured coating film was immersed in a 260 ° C. solder bath for 10 seconds to evaluate the coating film state once, and the test was repeated a total of five times. Judgment criteria are as follows.
○: Swelling, peeling, no discoloration, △: Slight swelling, peeling, discoloration, ×: Swelling, peeling, discoloration in most parts

(6) Solvent resistance Each substrate produced under the same conditions as in the evaluation item (4) was immersed in isopropyl alcohol at room temperature (23 ° C.) for 30 minutes, and an appearance was observed and a peeling test (JIS Z1522) was performed. Judgment criteria are as follows.
○: Swelling, peeling, no discoloration, △: Slight swelling, peeling, discoloration, ×: Swelling, peeling, discoloration in most parts

(7) Acid resistance Each substrate produced under the same conditions as in the evaluation item (4) was immersed in a 10% aqueous hydrochloric acid solution at room temperature (23 ° C.) for 30 minutes, and an appearance was observed and a peeling test (JIS Z1522) was performed. . Judgment criteria are as follows.
○: Swelling, peeling, no discoloration, △: Slight swelling, peeling, discoloration, ×: Swelling, peeling, discoloration in most parts

(8) Moisture resistance (PCT: Pressure cooker test)
The moisture resistance (PCT resistance) of each substrate produced under the same conditions as the evaluation item (4) was evaluated for the coating state after the coating film was continuously exposed for 50 hours under the conditions of 121 ° C., 100% RH and 2 atmospheres. did. The evaluation criteria are as follows.
○: Swelling, peeling, no discoloration, △: Swelling, peeling, discoloration, ×: Swelling, peeling, discoloration

(9) Thermal cycle test The thermal cycle test of each substrate produced under the same conditions as the evaluation item (4) was carried out by subjecting the obtained cured coating film to -65 ° C for 30 minutes and then to 125 ° C for 30 minutes. The test that was continuously exposed for 1 minute was performed for one cycle, and the test for a total of 100 cycles was continuously performed to evaluate the occurrence of cracks in the coating film.
○: No cracking or peeling, ×: Cracking or peeling, or both

  As is clear from the results in Table 1, the photosensitive thermosetting resin composition containing the polyfunctional epoxy (meth) acrylate compound of the present invention has a good balance of dryness to touch, alkali developability, and sensitivity. A cured coating film excellent in adhesion, solder heat resistance, solvent resistance, chemical resistance, moisture resistance (PCT resistance), and heat cycle characteristics required as a resist coating film can be provided. On the other hand, the resin composition of the comparative example cannot satisfy each evaluation in a well-balanced manner.

  Printed circuit boards for consumer and industrial printed wiring boards, and IC packages such as BGA (ball grid array) and CSP (chip scale package) using printed wiring boards with solder resist and sealing resin A liquid solder resist ink capable of forming an image with a dilute alkali developer used in the production of a wiring board, a polyfunctional epoxy (meth) acrylate compound useful for a dry film type solder resist, and the polyfunctional epoxy (meth) acrylate compound The present invention relates to a photosensitive thermosetting resin composition and a cured product thereof.

Claims (6)

A polybasic acid anhydride (a) is further added to the reaction product of the compound (a) having at least two epoxy groups in one molecule, the (meth) acrylic anhydride (b) and the unsaturated group-containing monocarboxylic acid (c). The following general formula [chemical formula 1] obtained by reacting d):

(In the formula, X represents a divalent aromatic group and / or an alkyl group and / or a cyclohexyl group, Y represents a divalent aromatic residue, and a dicarboxylic acid residue. M represents at least one of (meth) A carboxylic acid residue reacted with acrylic anhydride, and at least one is a residue of a polybasic acid anhydride containing one or more carboxyl groups, and the remainder represents a hydrogen atom. ) Represents a residue of (meth) acrylic acid produced by reaction of an acrylic anhydride with a hydroxyl group and a residue of an unsaturated group-containing monocarboxylic acid, where m is 0 to 100). Epoxy (meth) acrylate compound (A).   The polyfunctional epoxy (meth) acrylate compound (A) according to claim 1, wherein the polyfunctional epoxy (meth) acrylate compound (A) has an acid value in the range of 60 to 110 mgKOH / g.   The polyfunctional epoxy (meth) acrylate compound (A) according to claim 2, wherein 95% or more of the acid value is derived from a carboxyl group derived from a polybasic acid anhydride.   The polyfunctional epoxy (meth) acrylate compound (A) according to any one of claims 1 to 3, an epoxy compound (B) having two or more epoxy groups in one molecule, a photopolymerization initiator (C ), A diluent (D) as an essential component, a photosensitive thermosetting resin composition.   A cured product obtained by curing the photosensitive thermosetting resin composition according to claim 4. [Formula 2]:

(In the formula, X represents a divalent aromatic group and / or an alkyl group and / or a cyclohexyl group, Y represents a divalent aromatic residue, and a dicarboxylic acid residue. M represents at least one of (meth) A carboxylic acid residue reacted with acrylic anhydride, and at least one is a residue of a polybasic acid anhydride containing one or more carboxyl groups, and the remainder represents a hydrogen atom. ) Represents a residue of (meth) acrylic acid generated by reaction of an acrylic anhydride with a hydroxyl group and a residue of an unsaturated group-containing monocarboxylic acid, where m is 0 to 100. Polyfunctional epoxy (meth) acrylate compound.

Images