JPWO2018173679A1 - Acid group-containing (meth) acrylate resin and resin material for solder resist - Google Patents

Abstract

The present invention is an acid group-containing (meth) acrylate resin comprising an epoxy resin (A), an unsaturated monocarboxylic acid or a derivative thereof (B), and a polycarboxylic acid anhydride (C) as an essential reaction raw material, The acid group-containing (meth) acrylate resin is provided, wherein the epoxy resin (A) has an ester bond site derived from a polycarboxylic acid or its derivative (a1) in its molecular structure. The acid group-containing (meth) acrylate resin can form a cured product excellent in the balance between the degree of elongation and the heat resistance.

Description

  The present invention provides an acid group-containing (meth) acrylate resin which is excellent in the balance between elongation and heat resistance in a cured product, a curable resin composition containing the same, an insulating material comprising the curable resin composition, and solder resists The present invention relates to a resin material and a resist member.

  As a resin material for a solder resist for a printed wiring board, an acid group-containing epoxy acrylate resin obtained by reacting an acid anhydride with an acrylic acid after acrylateation of an epoxy resin with acrylic acid is widely used. The required performances for the solder resist resin material include various things such as curing with a small amount of exposure, excellent alkali developability, and excellent heat resistance and strength of the cured product, flexibility, dielectric characteristics and the like.

  As a conventionally known resin material for a solder resist, an acid obtained by further reacting acrylic acid and tetrahydrophthalic anhydride with a reaction product of a cresol novolac epoxy resin, a dicyclopentadiene type epoxy resin, and bisphenol F A group-containing epoxy acrylate resin is known (see Patent Document 1 below). Although the acid group-containing epoxy acrylate resin described in Patent Document 1 is characterized by being excellent in solder resistance and heat resistance in a cured product, the elongation in the cured product is very low, and the cured product is susceptible to cracking and inferior in reliability. There were problems such as being unsuitable for applications requiring flexibility, such as flexible substrates.

Japanese Patent Application Publication No. 2012-503690

  Therefore, the problem to be solved by the present invention is an acid group-containing (meth) acrylate resin which is excellent in the balance between the degree of elongation and the heat resistance in a cured product, a curable resin composition containing the same, and the curable resin composition Providing an insulating material, a resin material for solder resist, and a resist member.

  MEANS TO SOLVE THE PROBLEM As a result of conducting earnest examination, in order to solve the said subject, the present inventors molecular structure of the ester bond site | part derived from polycarboxylic acid or its derivative as an epoxy resin which is a reaction raw material of acid group containing epoxy (meth) acrylate resin. It has been found that by using the resin contained therein, the resin material is excellent in the balance between the elongation and the heat resistance in the cured product while maintaining the performance such as photosensitivity and alkali developability, and the present invention is completed. The

  That is, the present invention is an acid group-containing (meth) acrylate resin comprising an epoxy resin (A), an unsaturated monocarboxylic acid or its derivative (B), and a polycarboxylic acid anhydride (C) as an essential reaction raw material. The present invention relates to an acid group-containing (meth) acrylate resin in which the epoxy resin (A) has an ester bond site derived from a polycarboxylic acid or its derivative (a1) in its molecular structure.

  The present invention further relates to a curable resin composition containing the acid group-containing (meth) acrylate resin and a photopolymerization initiator.

  The present invention further relates to a cured product of the curable resin composition.

  The present invention further relates to an insulating material comprising the curable resin composition.

  The present invention further relates to a resin material for a solder resist comprising the curable resin composition.

  The present invention further relates to a resist member comprising the resin material for solder resist.

  According to the present invention, an acid group-containing (meth) acrylate resin excellent in the balance between elongation and heat resistance in a cured product, a curable resin composition containing the same, an insulating material comprising the curable resin composition, and a solder It is possible to provide a resin material for resist and a resist member.

FIG. 1 is a GPC chart of the acid group-containing (meth) acrylate resin (1) obtained in Example 1.

Hereinafter, the present invention will be described in detail.
The acid group-containing (meth) acrylate resin of the present invention comprises the epoxy resin (A), the unsaturated monocarboxylic acid or its derivative (B), and the polycarboxylic acid anhydride (C) as essential reaction raw materials, and the epoxy resin (A) is characterized by having an ester bond site derived from a polycarboxylic acid or its derivative (a1) in its molecular structure.

  In the present invention, the (meth) acrylate resin refers to a resin having an acryloyl group, a methacryloyl group, or both in the molecule. Moreover, a (meth) acryloyl group means one or both of an acryloyl group and a methacryloyl group, and a (meth) acrylate is a general term for an acrylate and a methacrylate.

  The epoxy resin (A) is characterized by having an ester bond site derived from polycarboxylic acid or its derivative (a1) in its molecular structure. The said characteristic is an essential requirement for obtaining the acid-group containing (meth) acrylate resin which is excellent in the balance of the elongation and heat resistance in hardened | cured material. If the said epoxy resin (A) has an ester bond site | part derived from polycarboxylic acid or its derivative (a1) in molecular structure, and if it has several epoxy groups in molecular structure, it is other specific. The structure is not particularly limited, and may be produced in any manner. As an example of the specific example of the said epoxy resin (A), the epoxy resin obtained by using the said polycarboxylic acid or its derivative (a1) and a raw material epoxy resin (a2) as an essential reaction raw material is mentioned.

  Examples of the polycarboxylic acid or its derivative (a1) include compounds having two or more carboxy groups in the molecular structure, and acid halides and acid anhydrides thereof. The specific structure of the polycarboxylic acid or its derivative (a1) is not particularly limited as long as it has two or more reactive points derived from a carboxy group and functions as a crosslinker by an ester bond, and various types are available. Compounds can be used. The number and type of carboxy group-derived functional groups possessed by the polycarboxylic acid or its derivative (a1) are appropriately selected according to the reactivity with the raw material epoxy resin (a2), the desired cured product performance, and the like. Among them, a dicarboxylic acid compound having two carboxy groups is preferable because it becomes an acid group-containing (meth) acrylate resin which is further excellent in the balance between the degree of elongation and the heat resistance in a cured product. As a specific example of a dicarboxylic acid compound, the compound etc. which are represented by following Structural formula (1) are mentioned.

（式中Ｘは脂肪族炭化水素基、脂環構造含有炭化水素基、芳香環含有炭化水素基、及びこれらが有する水素原子の一つ乃至複数がアルコキシ基、アリールオキシ基、ハロゲン原子等で置換された構造部位である。）

(Wherein X represents an aliphatic hydrocarbon group, an alicyclic structure-containing hydrocarbon group, an aromatic ring-containing hydrocarbon group, and one or more of the hydrogen atoms contained therein are substituted with an alkoxy group, an aryloxy group, a halogen atom, etc. Structural site))

  As for X in the structural formula (1), the aliphatic hydrocarbon group may be linear or branched, and may have one or more unsaturated bonds. Among them, an alkylene group having 1 to 6 carbon atoms is preferable because it becomes an acid group-containing (meth) acrylate resin which is further excellent in the balance between the degree of elongation and the heat resistance in a cured product. As an alicyclic structure which the said alicyclic structure containing hydrocarbon group has, a cyclopentane structure, a cyclohexane structure, a norbornane structure, a norbornene structure, a tricyclodecane structure, a dicyclopentadiene structure, an adamantane structure etc. are mentioned. If the alicyclic structure-containing hydrocarbon group has one or more of these alicyclic structures, it is an aliphatic hydrocarbon group as a bonding group of alicyclic structures or a bonding group of an alicyclic structure and a carboxy group. Etc. may be contained. The aliphatic hydrocarbon group as a bonding group is preferably an alkylene group having 1 to 6 carbon atoms. A benzene ring, a naphthalene ring, an anthracene ring etc. are mentioned as an aromatic ring structure which the said aromatic ring containing hydrocarbon group has. If the aromatic ring-containing hydrocarbon group has one or more of these aromatic rings, it contains an aliphatic hydrocarbon group or the like as a linking group between aromatic rings or a linking group between a fatty aromatic ring and a carboxy group. It may be done. The aliphatic hydrocarbon group as a bonding group is preferably an alkylene group having 1 to 6 carbon atoms. Further, examples of the alkoxy group include an alkoxy group having about 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, a propyloxy group, a butyloxy group, a pentyloxy group, and a hexyloxy group. Examples of the aryloxy group include a benzeneoxy group, a naphthyloxy group, and a structural moiety in which one or more of hydrogen atoms on the aromatic nucleus thereof are substituted with an aliphatic hydrocarbon group, an alkoxy group, a halogen atom or the like. Be As said halogen atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned.

  Among the dicarboxylic acid compounds, since it becomes an acid group-containing (meth) acrylate resin which is further excellent in the balance between the elongation and the heat resistance in the cured product, X in the structural formula (1) is an alicyclic structure-containing hydrocarbon It is preferable that one or more of the hydrogen atoms in the group or the alicyclic structure-containing hydrocarbon group be a structural moiety substituted with an alkoxy group, an aryloxy group, a halogen atom or the like. Furthermore, what has a cyclohexane structure as an alicyclic structure is more preferable.

  The specific structure is not particularly limited as long as the raw material epoxy resin (a2) is a resin having a plurality of epoxy groups, and a wide variety of resins can be used. Among them, those having an aromatic ring in the resin structure are preferable because they become an acid group-containing (meth) acrylate resin having particularly high heat resistance in a cured product. As an example, polyglycidyl ether of phenolic hydroxyl group containing resin etc. are mentioned. More specifically, for example, polyglycidyl ether of a novolac resin (hereinafter referred to as "raw epoxy resin (a2-1)") using one or more of phenolic hydroxyl group-containing compounds (P) as a reaction raw material, Reaction products containing one or more of the phenolic hydroxyl group-containing compounds (P) and the compounds (y) represented by any of the following structural formulas (y-1) to (y-5) as essential reaction raw materials Polyglycidyl ether (hereinafter referred to as “raw material epoxy resin (a2-2)”) and the like.

［式中ｈは０又は１である。Ｒ^１はそれぞれ独立して脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アリールオキシ基、アラルキル基の何れかであり、ｉは０又は１〜４の整数である。Ｚはビニル基、ハロメチル基、ヒドロキシメチル基、アルキルオキシメチル基の何れかである。Ｙは炭素原子数１〜４のアルキレン基、酸素原子、硫黄原子、カルボニル基の何れかである。ｊは１〜４の整数である。］

[Wherein, h is 0 or 1. R ¹ is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group or an aralkyl group, and i is an integer of 0 or 1 to 4. Z is any of a vinyl group, a halomethyl group, a hydroxymethyl group and an alkyloxymethyl group. Y is any of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom and a carbonyl group. j is an integer of 1 to 4; ]

  The phenolic hydroxyl group-containing compound (P) is, for example, phenol, polyhydroxybenzene, naphthol, polyhydroxynaphthalene, anthracenol, polyhydroxyanthracene, biphenol, bisphenol, and one or more of these aromatic nuclei. The compound etc. which have a substituent are mentioned. Examples of substituents on the aromatic nucleus include aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, aryl groups, aryloxy groups, and aralkyl groups. The aliphatic hydrocarbon group may be linear or branched and may have an unsaturated bond in its structure. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group and the like can be mentioned. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group and a butoxy group. The halogen atom may, for example, be a fluorine atom, a chlorine atom or a bromine atom. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a structural moiety in which the aliphatic hydrocarbon group, an alkoxy group, a halogen atom or the like is substituted on the aromatic nucleus thereof. Examples of the aryloxy group include a phenyloxy group, a naphthyloxy group, an anthryloxy group, and a structural moiety in which the alkyl group, an alkoxy group, a halogen atom or the like is substituted on the aromatic nucleus thereof. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, and a naphthylethyl group, and a structural moiety in which the above-mentioned alkyl group, alkoxy group, halogen atom or the like is substituted on the aromatic nucleus thereof. The above-mentioned phenolic hydroxyl group-containing compound (P) may be used alone or in combination of two or more. Above all, a compound having one or more substituents on an aromatic nucleus of phenol or phenol is obtained because it becomes an acid group-containing (meth) acrylate resin excellent in developability as well as elongation and heat resistance in a cured product. Preferably, phenol or an alkylphenol having one or more alkyl groups having 1 to 6 carbon atoms is preferable.

With respect to the compound (y), R ¹ in the structural formulas (y-1) to (y-5) is any of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, and an aralkyl group Specific examples thereof include those exemplified above. Among the compounds (y), the compound represented by the structural formula (y-1) is preferable because it becomes an acid group-containing (meth) acrylate resin which is further excellent in the balance of the elongation and heat resistance in a cured product.

  The novolac type resin which uses the said phenolic hydroxyl group containing compound (P) as a reaction raw material can be manufactured by the manufacturing method similar to general novolak resin. The molecular weight and the like of the novolac resin is preferably adjusted so that the softening point of the raw material epoxy resin (a2-1) to be obtained is about 50 to 120 ° C.

  The reaction of the phenolic hydroxyl group-containing compound (P) with the compound (y) can be carried out by a method of heating and stirring at a temperature of about 70 to 180 ° C. under an acid catalyst condition. The reaction ratio between the phenolic hydroxyl group-containing compound (P) and the compound (y) is 1.5 to 5 moles of the phenolic hydroxyl group-containing compound (P) with respect to 1 mole of the compound (y) Is preferred.

  The polyglycidyl etherification reaction of the said phenolic hydroxyl group containing resin can be performed by a well-known and usual method. As an example, for example, 2 to 10 moles of epihalohydrin per 1 mole of phenolic hydroxyl group contained in the phenolic hydroxyl group-containing resin is used, and the basicity is 0.9 to 2.0 moles per 1 mole of phenolic hydroxyl group The method of making it react at the temperature of 20-120 degreeC for 0.5 to 10 hours is mentioned, adding a catalyst at once or dividingly.

  The epoxy group equivalent of the raw material epoxy resin (a2) is in the range of 160 to 400 g / equivalent because it becomes an acid group-containing (meth) acrylate resin excellent in developability as well as elongation and heat resistance in a cured product Is preferred.

  The raw material epoxy resin (a2) may be used alone or in combination of two or more. Above all, it is preferable to use the raw material epoxy resin (a2-2) as an essential component because it becomes an acid group-containing (meth) acrylate resin which is further excellent in the balance of elongation and heat resistance in a cured product. Furthermore, in the obtained acid group-containing (meth) acrylate resin, various performances can be imparted in addition to the elongation and heat resistance in the cured product, and balance control of the respective performances becomes easy. It is preferable to use multiple types of epoxy resin as the epoxy resin (a2), and it is preferable to use the raw material epoxy resin (a2-1) and the raw material epoxy resin (a2-2) in combination.

  The ratio of the raw material epoxy resin (a2-2) to the total mass of the raw material epoxy resin (a2) is preferably 30% by mass or more, and more preferably 30 to 80% by mass, and 40 to 70. It is particularly preferable to be in the range of mass%. Moreover, it is preferable that the total mass of the said raw material epoxy resin (a2-1) and the said raw material epoxy resin (a2-2) with respect to the total mass of the said raw material epoxy resin (a2) is 50 mass% or more, 80 mass% It is more preferable that it is more than.

  When using two or more types together as said raw material epoxy resin (a2), you may mix | blend and use the raw material epoxy resin (a2) manufactured separately, respectively, It mix | blends at the stage of phenolic hydroxyl group containing resin, and polyglycidyl etherification is carried out. You may use what was.

  The reaction of the polycarboxylic acid or its derivative (a1) with the starting epoxy resin (a2) can be carried out, for example, in the presence of an esterification catalyst at a temperature range of 100 to 150 ° C. The reaction ratio between the polycarboxylic acid or its derivative (a1) and the raw material epoxy resin (a2) is an acid group-containing (meth) acrylate resin which is excellent in developability as well as elongation and heat resistance in a cured product Therefore, it is preferable to use the said polycarboxylic acid or its derivative (a1) in 0.5-20 mass% with respect to the gross mass of the said raw material epoxy resin (a2), and using in 1-10 mass% Is more preferred.

  Examples of the esterification reaction catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine and triphenylphosphine, and amine compounds such as triethylamine, tributylamine and dimethylbenzylamine. These may be used alone or in combination of two or more. The addition amount of the catalyst is preferably in the range of 0.05 to 5% by mass with respect to the total mass of the polycarboxylic acid or its derivative (a1) and the raw material epoxy resin (a2).

  The reaction of the polycarboxylic acid or its derivative (a1) with the starting epoxy resin (a2) may be carried out in an organic solvent, if necessary. The selection of the organic solvent to be used is appropriately selected depending on the reaction raw material and the solubility of the acid group-containing (meth) acrylate resin which is a product, and the reaction temperature conditions, for example, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, Examples thereof include methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate and the like. These may be used alone or in combination of two or more. The amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction materials, because the reaction efficiency is good.

  Moreover, as said epoxy resin (A), the epoxy resin which has an oxazolidone ring structure in molecular structure can also be used.

  If the epoxy resin having an oxazolidone ring structure in the molecular structure is a resin having an oxazolidone ring structure in the molecular structure, the specific structure, the production method and the like are not particularly limited, and various kinds of resins can be used. . As an example of the epoxy resin which has an oxazolidone ring structure in the said molecular structure, the polyglycidyl etherification thing of phenolic hydroxyl group containing compound (P) mentioned above and polyisocyanate compound (a3) are made into an essential reaction raw material, for example Reaction products are mentioned.

  As long as the polyisocyanate compound (a3) is a compound having a plurality of isocyanate groups in the molecule, its specific structure and the presence or absence of other functional groups are not particularly limited, and various kinds of compounds can be used. Specific examples of the polyisocyanate compound (a3) include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; Alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; and aromas such as tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, etc. Group diisocyanate compound; a polymer having a repeating structure represented by the following structural formula (2) Ren polyphenyl polyisocyanate; these isocyanurate modified product, a biuret modified product, and allophanate modified compounds and the like. These polyisocyanate compounds (a3) may be used alone or in combination of two or more.

［式中、Ｒ^１はそれぞれ独立に水素原子、炭素原子数１〜６の炭化水素基の何れかである。Ｒ^２はそれぞれ独立に炭素原子数１〜４のアルキル基、又は構造式（２）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｍは０又は１〜３の整数であり、ｌは１以上の整数である。］

[In formula, R < ¹ > is respectively independently a hydrogen atom and either a C1-C6 hydrocarbon group. R ² each independently represents an alkyl group having 1 to 4 carbon atoms, or a bonding point which is connected to a structural site represented by Structural Formula (2) via a methylene group marked with an asterisk (*). m is an integer of 0 or 1 to 3, and l is an integer of 1 or more. ]

  Examples of the unsaturated monocarboxylic acid or its derivative (B) include compounds having a (meth) acryloyl group and a carboxy group in one molecule such as acrylic acid and methacrylic acid, and acid halides and acid anhydrides thereof. Be These may be used alone or in combination of two or more.

  Any polycarboxylic acid anhydride (C) can be used as long as it is an acid anhydride of a compound having two or more carboxy groups in one molecule. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, There may be mentioned acid anhydrides of dicarboxylic acid compounds such as hexahydrophthalic acid and methylhexahydrophthalic acid. The polycarboxylic acid anhydrides (C) may be used alone or in combination of two or more. Among them, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyl hexahydrophthalic acid, etc., in the molecular structure, in terms of forming an acid group-containing (meth) acrylate resin having excellent heat resistance in a cured product. Acid anhydrides of compounds having a cyclic structure are preferred. Succinic anhydride is preferred in that the acid group-containing (meth) acrylate resin is excellent in developability.

  The acid group-containing (meth) acrylate resin of the present invention comprises the epoxy resin (A), the unsaturated monocarboxylic acid or its derivative (B), and the polycarboxylic acid anhydride (C) as essential reaction raw materials. If it is a thing, the manufacturing method will not be specifically limited, For example, the method of making all the reaction raw materials react at once, the method of making it react sequentially may be used. Among them, since the control of the reaction is easy, the epoxy resin (A) is reacted with the unsaturated monocarboxylic acid or its derivative (B) first, and then the polycarboxylic acid anhydride (C) is reacted. The method is preferred. The reaction is carried out, for example, by reacting the epoxy resin (A) with an unsaturated monocarboxylic acid or its derivative (B) in the presence of an esterification reaction catalyst in a temperature range of 100 to 150 ° C. It can carry out by the method etc. which add a polycarboxylic acid anhydride (C), and make it react in a temperature range of 90-120 degreeC. In addition, the production of the epoxy resin (A) and the production of the acid group-containing (meth) acrylate resin may be performed continuously.

  The reaction ratio between the epoxy resin (A) and the unsaturated monocarboxylic acid or its derivative (B) is such that the unsaturated monocarboxylic acid or its derivative (B) is used per 1 mol of epoxy group in the epoxy resin (A). It is preferable to use in the range of 0.9-1.1 mol. Moreover, it is preferable to use the reaction ratio of the said polycarboxylic acid anhydride (D) in 0.2-1.0 mol with respect to 1 mol of epoxy groups in an epoxy resin (A).

  Examples of the esterification catalyst include the same compounds as those used in the reaction of the polycarboxylic acid or its derivative (a1) with the raw material epoxy resin (a2). It is preferable to use the addition amount of a catalyst in the range of 0.03-5 mass% with respect to the total mass of the reaction raw material.

  The reaction may be carried out in an organic solvent, if necessary. Examples of the organic solvent to be used include the same compounds as those used in the reaction of the polycarboxylic acid or its derivative (a1) with the raw material epoxy resin (a2). The amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction materials, because the reaction efficiency is good.

  The acid value of the acid group-containing (meth) acrylate resin of the present invention is 40 to 90 mg KOH / g because it becomes an acid group-containing (meth) acrylate resin excellent in developability as well as elongation and heat resistance in a cured product. It is preferable to be in the range of In the present invention, the acid value of the acid group-containing (meth) acrylate resin is a value measured by the neutralization titration method of JIS K 0070 (1992).

  Since the acid group-containing (meth) acrylate resin of the present invention has a polymerizable (meth) acryloyl group in the molecular structure, for example, it is used as a curable resin composition by adding a photopolymerization initiator Can.

  As the photopolymerization initiator, an appropriate one may be selected and used depending on the type of active energy ray to be irradiated. Further, they may be used in combination with photosensitizers such as amine compounds, urea compounds, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds and nitrile compounds. Specific examples of the photopolymerization initiator include, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) Alkylphenone photopolymerization initiators such as -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; 2,4,6-trimethylbenzoyl-diphenyl- Acyl phosphine oxide type photoinitiators, such as a phosphine oxide; Intramolecular hydrogen abstraction type photoinitiators, such as a benzophenone compound, etc. are mentioned. These may be used alone or in combination of two or more.

  Commercial products of the photopolymerization initiator include, for example, “IRGACURE 127”, “IRGACURE 184”, “IRGACURE 250”, “IRGACURE 270”, “IRGACURE 290”, “IRGACURE 369E”, “IRGACURE 379 EG”, “IRGACURE 500”, “IRGACURE 651”, manufactured by BASF Corporation. “IRGACURE 754”, “IRGACURE 819”, “IRGACURE 907”, “IRGACURE 1173”, “IRGACURE 2959”, “IRGACURE MBF”, “IRGACURE TPO”, “IRGACURE OXE 01”, “IRGACURE OXE 02”, manufactured by IGM RESINS, Inc. , "OMNIRAD 250", "OMNIR D369 "," OMNIRAD369E "," OMNIRAD651 "," OMNIRAD907FF "," OMNIRAD1173 ", and the like.

  It is preferable that the addition amount of the said photoinitiator is a range of 0.05-15 mass% with respect to the sum total of components other than the solvent of curable resin composition, for example, the range of 0.1-10 mass% It is more preferable that

  The curable resin composition of the present invention may contain a resin component other than the acid group-containing (meth) acrylate resin of the present invention. The resin component can be obtained, for example, by reacting an epoxy resin such as a bisphenol epoxy resin or a novolac epoxy resin with (meth) acrylic acid, dicarboxylic acid anhydride, if necessary, unsaturated monocarboxylic acid anhydride, etc. Such resins include a resin having a carboxyl group and a (meth) acryloyl group in the resin, various (meth) acrylate monomers, and the like.

The (meth) acrylate monomer is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl ( Aliphatic mono (meth) acrylate compounds such as methyacrylate and octyl (meth) acrylate; alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate; Heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, phenylbenzyl ) Acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benzylbenzyl (meth) acrylate And mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds such as phenyl phenoxyethyl (meth) acrylate: (poly) oxyethylene chains in the molecular structure of the various mono (meth) acrylate monomers ) (Poly) oxyalkylene modified mono (meth) acrylate compounds into which a polyoxyalkylene chain such as an oxypropylene chain or (poly) oxy tetramethylene chain is introduced; various mono (meth) acrylate compounds described above (Poly) lactone-modified mono (meth) obtained by introducing a lactone structure acrylate compound in the molecular structure;

  Aliphatic di (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate 1,4-cyclohexanedimethanol di (meth) acrylate, norbornane di (meth) acrylate, norbornane dimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate Alicyclic di (meth) acrylate compounds such as, for example; aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylate and bisphenol di (meth) acrylate; various kinds of di (meth) acrylates Polyoxyalkylene-modified di (meth) acrylate compounds in which (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, (poly) oxytetramethylene chains are introduced into the molecular structure of the compound; Lactone-modified di (meth) acrylate compounds in which a (poly) lactone structure is introduced into the molecular structures of the various di (meth) acrylate compounds;

  Aliphatic tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and glycerin tri (meth) acrylate; (poly) oxyethylene chain in the molecular structure of the aliphatic tri (meth) acrylate compound, (poly) (Poly) oxyalkylene-modified tri (meth) acrylate compounds into which a (poly) oxyalkylene chain such as an oxypropylene chain or a (poly) oxytetramethylene chain has been introduced; in the molecular structure of the aliphatic tri (meth) acrylate compound ( A lactone-modified tri (meth) acrylate compound having a lactone structure introduced therein;

  A tetrafunctional or higher aliphatic poly (meth) acrylate compound such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; and the above-mentioned aliphatic poly (meth) acrylate compounds A tetrafunctional or higher (poly) oxyalkylene modified poly (meth) having a (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxy tetramethylene chain or the like introduced into the molecular structure Acrylate compounds; and tetrafunctional or higher lactone-modified poly (meth) acrylate compounds in which a (poly) lactone structure is introduced into the molecular structure of the aliphatic poly (meth) acrylate compound.

    The curable resin composition of the present invention may contain an organic solvent for the purpose of adjusting coating viscosity and the like. The type and addition amount thereof are appropriately adjusted according to the desired performance. Generally, it is used in 10-90 mass% with respect to the sum total of curable resin composition. Specific examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; esters such as methyl acetate, ethyl acetate and butyl acetate; and aromatics such as toluene and xylene Solvents; Alicyclic solvents such as cyclohexane and methylcyclohexane; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol and propylene glycol monomethyl ether; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol mono Examples include glycol ether solvents such as alkyl ether acetate. These may be used alone or in combination of two or more.

  The curable resin composition of the present invention may further contain various additives such as inorganic particles, polymer particles, pigments, antifoaming agents, viscosity modifiers, leveling agents, flame retardants, storage stabilizers and the like. .

  The acid group-containing (meth) acrylate resin of the present invention is characterized by being excellent in the balance between the degree of elongation and the heat resistance in a cured product. Generally, in order to increase the elongation of the cured product, it is necessary to introduce a flexible structure in the resin structure, but in this case, the heat resistance of the cured product tends to be significantly reduced. The acid group-containing (meth) acrylate resin of the present invention has a performance that reverses the conventional technical common knowledge in that both of these difficultly compatible performances are combined at a high level. The acid group-containing (meth) acrylate resin of the present invention is, for example, a solder resist, an interlayer insulating material, as a use in connection with semiconductor devices as a use in which the excellent property of the balance between elongation and heat resistance in a cured product is used. It can be used as a package adhesion layer of a package material, an underfill material, a circuit element or the like, or an adhesion layer of an integrated circuit element and a circuit substrate. Moreover, as thin-film display related applications represented by LCD and OELD, it can be suitably used for thin film transistor protective film, liquid crystal color filter protective film, pigment resist for color filter, resist for black matrix, spacer and the like.

  Moreover, since the acid group-containing (meth) acrylate resin of the present invention is excellent not only in elongation and heat resistance in a cured product but also in developability, it can be suitably used for solder resist applications. The resin material for a solder resist of the present invention contains, for example, each component such as a curing agent, a curing accelerator, an organic solvent, etc. in addition to the acid group-containing (meth) acrylate resin, a photopolymerization initiator and various additives. Become.

  The curing agent is not particularly limited as long as it has a functional group capable of reacting with the carboxy group in the acid group-containing (meth) acrylate resin, and examples thereof include epoxy resins. The epoxy resin used here is, for example, bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin Bisphenol novolac epoxy resin, naphthol novolac epoxy resin, naphthol-phenol co-convoluted novolak epoxy resin, naphthol-cresol co-convoluted novolac epoxy resin, phenol aralkyl epoxy resin, naphthol aralkyl epoxy resin, dicyclopentadiene-phenol An addition reaction type epoxy resin etc. are mentioned. These may be used alone or in combination of two or more. Among these epoxy resins, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-contracted novolac type epoxy resin from the viewpoint of excellent heat resistance in cured products. Novolak-type epoxy resins such as naphthol-cresol co-contracted novolac-type epoxy resins are preferable, and those having a softening point in the range of 50 to 120 ° C. are particularly preferable.

  The curing accelerator accelerates the curing reaction of the curing agent, and when an epoxy resin is used as the curing agent, a phosphorus compound, tertiary amine, imidazole, metal salt of organic acid, Lewis acid, Amine complex salts and the like can be mentioned. These may be used alone or in combination of two or more. The addition amount of the curing accelerator is, for example, in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent.

  The organic solvent is not particularly limited as long as it can dissolve various components such as the acid group-containing (meth) acrylate resin and the curing agent, and examples thereof include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, Examples thereof include cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate.

  In the method for obtaining a resist member using the resin material for solder resist of the present invention, for example, the resin material for solder resist is applied onto a substrate, and the organic solvent is volatilized and dried in a temperature range of about 60 to 100 ° C. After that, it is exposed to ultraviolet light, electron beam or the like through a photo mask on which a desired pattern is formed, and the unexposed area is developed with an alkaline aqueous solution, and further heat curing is performed at a temperature range of about 140 to 180 ° C. .

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples.

  The acid value of the acid group-containing (meth) acrylate resin in Examples of the present application was measured by the neutralization titration method of JIS K 0070 (1992).

Production Example 1 Production of Epoxy Resin (A-1) In a four-necked flask equipped with a thermometer, a stirrer and a condenser, 376 g of bisphenol A type epoxy resin ("EPICLON 850S" epoxy equivalent 188 g / eq equivalent made by DIC Corporation), 6.6 g of bisphenol A and 0.08 g of tetrabutylphosphonium bromide ("TBP-BB" manufactured by Hokuko Chemical Co., Ltd.) were charged, and the temperature was raised to 150 ° C. for reaction for 2 hours. Subsequently, 58 g of tolylene diisocyanate ("TDI-80" manufactured by Mitsui Chemicals, Inc.) was dropped over 3 hours under the same temperature conditions. Heating and stirring are continued even after completion of dropping, and sampling is performed with time and IR measurement is performed to confirm that the absorption peak of the isocyanate group (near 2250 to 2280 cm ^-1 ) disappears, and it has an oxazolidone ring structure in the molecule 431 g of epoxy resin (A-1) was obtained. The epoxy equivalent of the obtained epoxy resin (A-1) is 338 g / equivalent, the softening point measured based on JIS K 7234 is 79 ° C., according to ASTM D 4287, and the melt viscosity at 150 ° C. measured with an ICI viscometer It was 6.3 dPa · s.

Example 1 Production of Acid Group-Containing (Meth) Acrylate Resin (1) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 274 g of diethylene glycol monomethyl ether acetate, "EPICLON HP-7200 L" manufactured by DIC Corporation Polyglycidyl ether of cyclopentadiene addition type phenol resin, epoxy group equivalent 248 g / equivalent) 300 g, DIC Corporation "EPICLON N-695" (cresol novolac epoxy resin, epoxy group equivalent 215 g / equivalent) 300 g and 1,4- After 41 g of cyclohexanedicarboxylic acid, 1.6 g of dibutylhydroxytoluene and 1.9 g of triphenylphosphine were added and dissolved, they were reacted under a nitrogen atmosphere at 120 ° C. for 3 hours. 0.4 g of methoquinone, 45 g of acrylic acid and 0.5 g of triphenylphosphine were added, and reaction was carried out at 120 ° C. for 15 hours while blowing in air. Further, 345 g of diethylene glycol monomethyl ether acetate and 217 g of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 5 hours to obtain a target acid group-containing (meth) acrylate resin (1) solution. The solid content acid value of the acid group-containing (meth) acrylate resin (1) was 80 mg KOH / g. A GPC chart of the acid group-containing (meth) acrylate resin (1) is shown in FIG.

Example 2 Production of Acid Group-Containing (Meth) Acrylate Resin (2) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 274 g of diethylene glycol monomethyl ether acetate, "EPICLON HP-7200 L" manufactured by DIC Corporation Polyglycidyl ether of cyclopentadiene addition type phenol resin, epoxy group equivalent 248 g / equivalent) 300 g, DIC Corporation "EPICLON N-695" (cresol novolac epoxy resin, epoxy group equivalent 215 g / equivalent) 300 g and 1,4- After 41 g of cyclohexanedicarboxylic acid, 1.6 g of dibutylhydroxytoluene and 1.9 g of triphenylphosphine were added and dissolved, they were reacted under a nitrogen atmosphere at 120 ° C. for 3 hours. 0.4 g of methoquinone, 45 g of acrylic acid and 0.5 g of triphenylphosphine were added, and reaction was carried out at 120 ° C. for 15 hours while blowing in air. Furthermore, 291 g of diethylene glycol monomethyl ether acetate and 130 g of succinic anhydride were added and reacted at 110 ° C. for 5 hours to obtain a target acid group-containing (meth) acrylate resin (2) solution. The solid content acid value of the acid group-containing (meth) acrylate resin (2) was 80 mg KOH / g.

Example 3 Production of Acid Group-Containing (Meth) Acrylate Resin (3) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 334 g of diethylene glycol monomethyl ether acetate, "EPICLON HP-7200 L" manufactured by DIC Corporation Polyglycidyl ether of cyclopentadiene addition type phenol resin, epoxy group equivalent 248 g / equivalent) 369 g, epoxy resin (A-1) 369 g obtained in Production Example 1, 41 g of 1,4-cyclohexanedicarboxylic acid, dibutyl hydroxytoluene 1.9 g Then, 2.3 g of triphenylphosphine was added and dissolved, and then reacted under a nitrogen atmosphere at 120 ° C. for 3 hours. 0.5 g of methoquinone, 152 g of acrylic acid and 0.5 g of triphenyl phosphine were added, and reaction was carried out at 120 ° C. for 10 hours while blowing in air. Furthermore, 225 g of diethylene glycol monomethyl ether acetate and 256 g of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 5 hours to obtain a target acid group-containing (meth) acrylate resin (2) solution. The solid content acid value of the acid group-containing (meth) acrylate resin (3) was 80 mg KOH / g.

Comparative Production Example 1 Production of Acid Group-Containing (Meth) Acrylate Resin (1 ′) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 101 g of diethylene glycol monomethyl ether acetate, “EPICLON N-680” manufactured by DIC Corporation (Cresol novolac type epoxy resin, epoxy group equivalent 214 g / equivalent) 428 g, dibutyl hydroxytoluene 4 g, and methoquinone 0.4 g were added and dissolved. Further, 144 g of acrylic acid and 1.6 g of triphenyl phosphine were added, and the esterification reaction was carried out at 120 ° C. for 10 hours while blowing in air. Thereafter, 311 g of diethylene glycol monomethyl ether acetate and 160 g of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain an acid group-containing (meth) acrylate resin (1 ′). The solid content acid value of the acid group-containing (meth) acrylate resin (1 ′) was 54.4 mg KOH / g.

Examples 4 to 6 and Comparative Example 1
A curable resin composition was prepared in the following manner, and various evaluation tests were conducted. The results are shown in Table 1.

Evaluation of heat resistance and elongation of cured product Preparation of curable resin composition 100 g of the acid group-containing (meth) acrylate resin obtained above, "EPICLON N-680" (cresol novolac epoxy resin) manufactured by DIC Corporation A curable resin composition comprising 24 g of "IRGACURE 907" [2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one] manufactured by BASF, 5 g of diethylene glycol monomethyl ether acetate and 13 g of diethylene glycol monomethyl ether acetate Obtained.

Preparation of Cured Product The curable resin composition was applied on a glass substrate with a 50 μm applicator and dried at 80 ° C. for 30 minutes. After irradiation with ultraviolet light of 1000 mJ / cm ² using a metal halide lamp, the cured product was peeled from the glass substrate by heating at 160 ° C. for 1 hour to obtain a cured product.

Evaluation of heat resistance of cured product A 6 mm × 40 mm test piece is cut out of the cured product, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Rheometrics Co., tension method: frequency 1 Hz, heating rate 3) The temperature at which the change in elastic modulus is maximum (the largest change in tan δ) is regarded as the glass transition temperature (Tg), and the heat resistance is evaluated according to the following criteria.
A: Glass transition temperature (Tg) is 130 ° C. or more B: Glass transition temperature (Tg) is less than 130 ° C.

Evaluation of Elongation of Cured Material A test piece of 10 mm × 80 mm is cut out of the cured material, and the elongation is measured under the following conditions using a tensile test apparatus (“Sensitivity universal tester autograph AG-IS” manufactured by Shimadzu Corporation) And evaluated.
Temperature 23 ° C, humidity 50%, marked line distance 20 mm, fulcrum distance 20 mm, tensile speed 10 mm / min A: Elongation 3.5% or more B: Elongation 3% or more and less than 3.5% C: Elongation Degree is less than 3%

Evaluation of photosensitivity Preparation of a curable resin composition 100 g of the acid group-containing (meth) acrylate resin obtained above, 24 g of "EPICLON N-680" (cresol novolac epoxy resin) manufactured by DIC Corporation, Toagosei Co., Ltd. 10 g of “Lumicure DPA-600T” (composition containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate at a molar ratio of 40/60) “IRGACURE 907” [2-methyl-1- (4) manufactured by BASF Corp. -Methylthiophenyl) -2-morpholinopropan-1-one] 5 g, 13 g of diethylene glycol monomethyl ether acetate, and 0.65 g of phthalocyanine green as a pigment were blended and kneaded with a roll mill to obtain a curable resin composition.

-Measurement of light sensitivity The curable resin composition was applied on a glass substrate with a 50 μm applicator and dried at 80 ° C for 30 minutes. Next, step tablets No. A UV light of 500 mJ / cm ² was irradiated using a metal halide lamp through 2. This was developed with a 1% by mass aqueous sodium carbonate solution for 180 seconds, and the number of remaining stages was evaluated. The greater the number of remaining stages, the higher the light sensitivity.

Claims (10)

  An acid group-containing (meth) acrylate resin comprising an epoxy resin (A), an unsaturated monocarboxylic acid or a derivative thereof (B), and a polycarboxylic acid anhydride (C) as an essential reaction raw material, comprising the epoxy resin ( An acid group-containing (meth) acrylate resin, wherein A) has an ester bond site derived from a polycarboxylic acid or its derivative (a1) in its molecular structure.   The acid group-containing (meth) acrylate resin according to claim 1, wherein the epoxy resin (A) contains the polycarboxylic acid or its derivative (a1) and a raw material epoxy resin (a2) as essential reaction raw materials.   The acid group-containing (meth) acrylate resin according to claim 2, wherein plural kinds of epoxy resins are used as the raw material epoxy resin (a2). As said raw material epoxy resin (a2), 1 type or multiple types of phenolic hydroxyl group containing compound (P), and following Structural formula (y-1)-(y-5)

[Wherein, h is 0 or 1. R ¹ is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group or an aralkyl group, and i is an integer of 0 or 1 to 4. Z is any of a vinyl group, a halomethyl group, a hydroxymethyl group and an alkyloxymethyl group. Y is any of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom and a carbonyl group. j is an integer of 1 to 4; ]
3. The acid group-containing (meth) acrylate according to claim 2, wherein a polyglycidyl ether (raw material epoxy resin (a2-2)) of a reaction product, which contains the compound (y) represented by any one of the above as an essential reaction raw material resin.   The acid group-containing (meth) acrylate resin according to claim 4, wherein 30% by mass or more of the raw material epoxy resin (a2) is the raw material epoxy resin (a2-2).   A curable resin composition comprising the acid group-containing (meth) acrylate resin according to any one of claims 1 to 5 and a photopolymerization initiator.   A cured product of the curable resin composition according to claim 6.   An insulating material comprising the curable resin composition according to claim 6.   The resin material for solder resists which consists of a curable resin composition of Claim 6.   A resist member comprising the resin material for a solder resist according to claim 9.

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