TW201840625A - Acid-group-containing (meth)acrylate resin and resin material for solder resist - Google Patents

Abstract

The present invention provides an acid-group-containing (meth)acrylate resin obtained from starting materials which comprises (A) an epoxy resin, (B) an unsaturated monocarboxylic acid or a derivative thereof, and (C) a polycarboxylic anhydride as essential reactants, wherein the epoxy resin (A) has a molecular structure which contains an ester bond portion derived from (a1) a polycarboxylic acid or a derivative thereof. This acid-group-containing (meth)acrylate resin can give cured objects having an excellent balance between elongation and heat resistance.

Description

 (meth) acrylate resin containing acid group and resin material for solder resist  

The present invention relates to an acid group-containing (meth) acrylate resin excellent in a balance between elongation and heat resistance of a cured product, a curable resin composition containing the same, an insulating material containing the curable resin composition, and a solder resist Resin materials and solder resist members are used.

In the resin material for solder resist for printed wiring boards, an acid group-containing epoxy acrylate resin obtained by acrylizing an epoxy resin with acrylic acid and reacting with an acid anhydride is widely used. The properties required for the resin material for solder resist welding include various types such as curing with a small amount of exposure, excellent alkali developability, heat resistance or strength of a cured product, flexibility, and dielectric properties.

As a resin material for solder resists known in the prior art, a reaction product of a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, and a bisphenol F is known, and further with acrylic acid and tetrahydroanthracene. An acid group-containing epoxy acrylate resin obtained by an acid anhydride reaction (see Patent Document 1 below). The epoxy acrylate resin containing an acid group described in Patent Document 1 has characteristics of excellent solder resistance and heat resistance of a cured product, but the elongation of the cured product is extremely low, and the cured product is likely to be cracked, resulting in poor reliability. It is not suitable for problems such as applications requiring flexibility such as flexible substrates.

 [Previous Technical Literature]    [Patent Literature]  

[Patent Document 1] Japanese Patent Publication No. 2012-503690

Therefore, the object of the present invention is to provide an acid group-containing (meth) acrylate resin excellent in the balance between elongation and heat resistance of a cured product, and a curable resin composition containing the same, which comprises the aforementioned curability. Insulating material of resin composition, resin material for solder resist, and solder resist member.

The inventors of the present invention have found that the epoxy resin as a reaction raw material of an epoxy group (meth) acrylate resin containing an acid group has a polycarboxylic acid derived from a molecular structure or The ester bond portion of the derivative can be used as a resin material which is excellent in the balance between the elongation of the cured product and the heat resistance while maintaining the properties such as light sensitivity or alkali developability, and the present invention has been completed.

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

Furthermore, the present invention relates to a curable resin composition comprising the above-mentioned acid group-containing (meth) acrylate resin and a photopolymerization initiator.

Furthermore, the present invention relates to a cured product of the above curable resin composition.

Furthermore, the present invention relates to an insulating material comprising the above-described curable resin composition.

Furthermore, the present invention relates to a resin material for solder resist containing the curable resin composition.

Furthermore, the present invention relates to a solder resist member including the above-described resin material for solder resist.

According to the present invention, an acid group-containing (meth) acrylate resin excellent in a balance between elongation and heat resistance of a cured product, a curable resin composition containing the same, and an insulating material containing the curable resin composition described above can be provided. , solder resist resin material and solder resist member.

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

 [Formation of the Invention]  

Hereinafter, the present invention will be described in detail.

The acid group-containing (meth) acrylate resin of the present invention is characterized by using an epoxy resin (A), an unsaturated monocarboxylic acid or a derivative thereof (B), and a polycarboxylic acid anhydride (C) as essential reactions A raw material in which the aforementioned epoxy resin (A) has an ester bond site derived from a polycarboxylic acid or a derivative (a1) in a molecular structure.

In the present invention, the (meth) acrylate resin means a resin having an acryl fluorenyl group, a methacryl fluorenyl group, or both in the molecule. Further, the (meth)acrylonitrile group means one or both of an acryloyl group and a methacryl group, and a (meth) acrylate is a general term of an acrylate and a methacrylate.

The above epoxy resin (A) is characterized in that it has an ester bond moiety derived from a polycarboxylic acid or a derivative (a1) in its molecular structure. This characteristic is a requirement for obtaining an acid group-containing (meth) acrylate resin which is excellent in the balance between the elongation of the cured product and the heat resistance. The epoxy resin (A) is not particularly limited as long as it has an ester bond site derived from a polycarboxylic acid or a derivative (a1) in its molecular structure and has a plurality of epoxy groups in its molecular structure. It can be manufactured by any means. An example of a specific example of the epoxy resin (A) is an epoxy resin obtained by using the polycarboxylic acid or a derivative thereof (a1) and a raw material epoxy resin (a2) as essential reaction materials.

The polycarboxylic acid or the derivative (a1) thereof may, for example, be a compound having two or more carboxyl groups in its molecular structure, or an acid halide or an acid anhydride thereof. The polycarboxylic acid or its derivative (a1) is not particularly limited as long as it has two or more reaction sites derived from a carboxyl group and has an ester bond as a crosslinking agent, and various compounds can be used. . The amount or type of the functional group derived from the carboxyl group which the polycarboxylic acid or the derivative (a1) has is appropriately selected depending on the reactivity with the raw material epoxy resin (a2) or the desired properties of the cured product. Among them, the acid group-containing (meth) acrylate resin which is more excellent in the balance between the elongation of the cured product and the heat resistance is preferably a dicarboxylic acid compound having two carboxyl groups. Specific examples of the dicarboxylic acid compound include compounds represented by the following structural formula (1).

HOOC-X-COOH (1)

(wherein X is an aliphatic hydrocarbon group, a hydrocarbon group having an alicyclic structure, a hydrocarbon group containing an aromatic ring, and a structure in which one or more of the hydrogen atoms contained therein are substituted with an alkoxy group, an aryloxy group, a halogen atom or the like Part).

With respect to X in the above structural formula (1), the above aliphatic hydrocarbon group may be a linear type or a branched type, and may have one to a plurality of unsaturated bonds. Among them, the acid group-containing (meth) acrylate resin which is more excellent in the balance between the elongation and the heat resistance of the cured product is preferably an alkylene group having 1 to 6 carbon atoms. Examples of the alicyclic structure of the hydrocarbon group having an alicyclic structure include a cyclopentane structure, a cyclohexane structure, a norbornane structure, a norbornene structure, a tricyclodecane structure, and dicyclopentadiene. Structure, adamantane structure, etc. The hydrocarbon group having an alicyclic structure may contain an aliphatic hydrocarbon group or the like as a bonding group of an alicyclic structure or a bonding group of an alicyclic structure and a carboxyl group as long as it has one to a plurality of such alicyclic structures. The aliphatic hydrocarbon group as a bonding group is preferably an alkylene group having 1 to 6 carbon atoms. The aromatic ring structure of the hydrocarbon group containing an aromatic ring may, for example, be a benzene ring, a naphthalene ring or an anthracene ring. The hydrocarbon group containing an aromatic ring may contain, as long as it has one or more of these aromatic rings, an aliphatic hydrocarbon group or the like as a bonding group of an aromatic ring or a bonding group of a fatty aromatic ring and a carboxyl group. 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 alkoxy groups having a carbon number of about 1 to 6 such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group or a hexyloxy group. Examples of the aryloxy group include a phenoxy group, a naphthyloxy group, and one of a plurality of hydrogen atoms on the aromatic nucleus to a plurality of structural sites substituted with an aliphatic hydrocarbon group, an alkoxy group, a halogen atom or the like. Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.

Among the dicarboxylic acid compounds, the acid group-containing (meth) acrylate resin which is more excellent in the balance between the elongation and the heat resistance of the cured product, the X in the above structural formula (1) contains an alicyclic ring. It is preferred that one of a hydrocarbon group of a structure or a hydrogen atom in a hydrocarbon group containing an alicyclic structure is substituted with a plurality of structural sites substituted with an alkoxy group, an aryloxy group, a halogen atom or the like. Further, in terms of the alicyclic structure, it is more preferable to have a cyclohexane structure.

The raw material epoxy resin (a2) is not particularly limited as long as it is a resin having a plurality of epoxy groups, and various types can be used. Among them, a (meth) acrylate resin containing an acid group which is particularly high in heat resistance of a cured product preferably has an aromatic ring in a resin structure. An example of this may be a polyepoxypropyl ether or the like which contains a phenolic hydroxyl group-containing resin. More specifically, for example, polyepoxypropyl ether of a novolak type resin containing one or more kinds of the phenolic hydroxyl group-containing compound (P) as a reaction raw material (hereinafter referred to as "raw material epoxy resin (a2) -1)"), or a compound (y) represented by any one of the following structural formulae (y-1) to (y-5) as one of a compound (P) containing a phenolic hydroxyl group; The polyepoxypropyl ether of the reaction product of the reaction raw material (hereinafter referred to as "raw material epoxy resin (a2-2)") or the like.

Wherein h is 0 or 1; R ^{1 is} independently, and is any of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group; i is an integer of 0 or 1 to 4 ; Z is any one of a vinyl group, a halomethyl group, a methylol group, or an alkoxymethyl group; Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom or a carbonyl group; An integer from 1 to 4].

The phenolic hydroxyl group-containing compound (P) may, for example, be phenol, polyhydroxybenzene, naphthol, polyhydroxynaphthalene, indophenol, polyhydroxyindole, biphenol or bisphenol. A compound having one to a plurality of substituents and the like. Examples of the substituent on the aromatic nucleus include an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, an aralkyl group and the like. The aliphatic hydrocarbon group may be either a linear type or a branched type, and may have an unsaturated bond in the structure. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a structural moiety on the aromatic nucleus substituted with the above aliphatic hydrocarbon group, alkoxy group, halogen atom or the like. Examples of the aryloxy group include a phenoxy group, a naphthyloxy group, a decyloxy group, and a structural moiety on the aromatic nucleus substituted with the above-mentioned alkyl group, alkoxy group, halogen atom or the like. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a structural moiety on the aromatic nucleus substituted with the above alkyl group, an alkoxy group, a halogen atom or the like. The phenolic hydroxyl group-containing compound (P) may be used alone or in combination of two or more. Among them, in addition to the elongation or heat resistance of the cured product, the acid group-containing (meth) acrylate resin excellent in developability has one to a plurality of substitutions with phenol or an aromatic nucleus of phenol. The compound of the group is preferably a phenol or an alkylphenol having one to a plurality of alkyl groups having 1 to 6 carbon atoms.

With respect to the above compound (y), R ¹ in the above structural formula (y-1) to (y-5) is an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group or an aralkyl group. For one of the specific examples, the former example or the like can be cited. Among the above-mentioned compounds (y), the acid group-containing (meth) acrylate resin which is more excellent in the balance between the elongation and the heat resistance of the cured product is a compound represented by the above structural formula (y-1). It is better.

The novolac type resin containing the phenolic hydroxyl group-containing compound (P) as a reaction raw material can be produced in the same manner as a general novolak resin. The molecular weight of the novolac type resin or the like is preferably adjusted so that the softening point of the obtained raw material epoxy resin (a2-1) is about 50 to 120 °C.

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

The polyepoxypropyl etherification reaction of the phenolic hydroxyl group-containing resin can be carried out by a conventionally known method. In one example, for example, a phenolic hydroxyl group having a phenolic hydroxyl group-containing resin of 1 mole is used, and 2 to 10 moles of epihalohydrin is used, which is relative to 1 mole. A 0.9 to 2.0 molar alkaline catalyst of a phenolic hydroxyl group is added once or in portions, and a reaction is carried out at a temperature of 20 to 120 ° C for 0.5 to 10 hours.

The epoxy group equivalent of the raw material epoxy resin (a2) is an acid group-containing (meth)acrylate resin which is excellent in developability in addition to the elongation and heat resistance of the cured product, and is 160~ A range of 400 g/equivalent is preferred.

The raw material epoxy resin (a2) may be used alone or in combination of two or more. Among them, the acid group-containing (meth) acrylate resin which is more excellent in the balance between the elongation of the cured product and the heat resistance is preferably the use of the above-mentioned raw material epoxy resin (a2-2) as an essential component. . Further, in the obtained acid group-containing (meth) acrylate resin, various properties can be imparted in addition to the elongation or heat resistance of the cured product, and the balance control of various properties becomes easy. As the raw material epoxy resin (a2), a plurality of epoxy resins are preferably used, and the raw material epoxy resin (a2-1) and the raw material epoxy resin (a2-2) are preferably used in combination.

The ratio of the raw material epoxy resin (a2-2) is preferably 30% by mass or more, more preferably 30% to 80% by mass, based on the total mass of the raw material epoxy resin (a2). The range of ~70% by mass is particularly good. In addition, the total mass of the raw material epoxy resin (a2-1) and the raw material epoxy resin (a2-2) is preferably 50% by mass or more based on the total mass of the raw material epoxy resin (a2). More than 80% by mass is more preferable.

In the case where the above-mentioned raw material epoxy resin (a2) is used in combination, the raw material epoxy resin (a2) which is separately produced may be blended and used, or may be blended at the stage of the resin containing a phenolic hydroxyl group. Conducting polyepoxypropyl etherification.

The reaction of the polycarboxylic acid or its derivative (a1) with the raw material epoxy resin (a2) can be carried out, for example, in the presence of an esterification catalyst at a temperature ranging from 100 to 150 °C. The reaction ratio of the polycarboxylic acid or its derivative (a1) to the raw material epoxy resin (a2) is an acid group-containing (methyl) which is excellent in developability in addition to the elongation or heat resistance of the cured product. The acrylate resin is preferably used in an amount of from 0.5 to 20% by mass based on the total mass of the raw material epoxy resin (a2), or a derivative (a1) thereof. A range of ~10% by mass is more preferable.

The esterification reaction catalyst may, for example, be a phosphorus compound such as trimethylphosphine, tributylphosphine or triphenylphosphine; or an amine compound such as triethylamine, tributylamine or dimethylbenzylamine. These may be used individually or in combination of 2 or more types. The amount of the catalyst added is preferably from 0.05 to 5% by mass based on the total mass of the polycarboxylic acid or its derivative (a1) and the raw material epoxy resin (a2).

The reaction of the above polycarboxylic acid or its derivative (a1) with the raw material epoxy resin (a2) may be carried out in an organic solvent as needed. The selection of the organic solvent to be used may be appropriately selected depending on the solubility of the reaction raw material and the acid group-containing (meth) acrylate resin or the reaction temperature conditions, and examples thereof include methyl ethyl ketone and acetone. , dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl sarbuta, dialkyl diol monoalkyl ether acetate, dialkyl alkyl Alcohol acetate and the like. These may be used individually or in combination of two or more types. The amount of the organic solvent to be used is preferably from about 0.1 to 5 times the total mass of the reaction raw materials in order to improve the reaction efficiency.

Further, in the case of the above epoxy resin (A), it is also possible to use a molecular structure An epoxy resin having an oxazolidine ring structure.

Having the aforementioned molecular structure An oxazolidinone ring structure epoxy resin as long as it has a molecular structure The specific structure or production method of the oxazolidinone ring structure is not particularly limited, and various types can be used. With the aforementioned molecular structure An example of the epoxy resin of the oxazolidinone ring structure is, for example, a polyepoxypropyl etherate compound and a polyisocyanate compound (a3) containing the phenolic hydroxyl group-containing compound (P) as an essential reaction material. Reaction product.

The polyisocyanate compound (a3) is not particularly limited as long as it is a compound having a plurality of isocyanato groups in the molecule, and the specific structure or presence or absence of other functional groups is not particularly limited, and various types can be used. Specific examples of the polyisocyanate compound (a3) include butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4. An aliphatic diisocyanate compound such as 4-trimethylhexamethylene diisocyanate; an alicyclic diisocyanate such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate or hydrogenated diphenylmethane diisocyanate; a compound; an aromatic diisocyanate compound such as methyl phenyl diisocyanate, xylene diisocyanate, tetramethyl xylene diisocyanate, diphenylmethane diisocyanate or 1,5-naphthalene diisocyanate; having the following structural formula ( 2) A polymethylene polyphenyl polyisocyanate having a repeating structure as shown; such a meta-cyanate modified body, a biuret modified body, a urea modified body, or the like. These polyisocyanate compounds (a3) may be used alone or in combination of two or more.

[wherein R ^{1 is} independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; and R ^{2 is} independently an alkyl group having 1 to 4 carbon atoms or a sub-marker attached thereto; Any one of the connection points connecting the base to the structural part represented by the structural formula (2); m is an integer of 0 or 1 to 3, and l is an integer of 1 or more].

The unsaturated monocarboxylic acid or the derivative (B) thereof may, for example, be a compound having a (meth)acryloyl group and a carboxyl group in one molecule such as acrylic acid or methacrylic acid, or an acid halide or an acid anhydride thereof. These may be used individually or in combination of 2 or more types.

The polycarboxylic acid anhydride (C) may be any acid anhydride as long as it is a compound having two or more carboxyl groups in one molecule. Specific examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, sebacic acid, maleic acid, fumaric acid, and citric acid. An acid anhydride of a dicarboxylic acid compound such as isophthalic acid, terephthalic acid, tetrahydrofurfuric acid, hexahydrophthalic acid or methylhexahydrophthalic acid. The polycarboxylic acid anhydride (C) may be used alone or in combination of two or more. Among them, from the viewpoint of an acid group-containing (meth) acrylate resin excellent in heat resistance of a cured product, citric acid, isophthalic acid, terephthalic acid, tetrahydrofurfuric acid, hexahydrofurfuric acid, An acid anhydride such as methyl hexamethylene hydride or the like having a cyclic structure in a molecular structure is preferred. Further, from the viewpoint of an acid group-containing (meth) acrylate resin excellent in developability, succinic anhydride is preferred.

The acid group-containing (meth) acrylate resin of the present invention is required to contain the epoxy resin (A), the unsaturated monocarboxylic acid or a derivative thereof (B), and the polycarboxylic acid anhydride (C) as essential. The method of producing the raw material is not particularly limited. For example, it may be a method of reacting the reaction raw materials all at once, or may be a method of sequentially reacting them. Among them, from the viewpoint of easy control of the reaction, it is preferred to first react the epoxy resin (A) with an unsaturated monocarboxylic acid or a derivative thereof (B), and then react with the polycarboxylic acid anhydride (C). . The reaction can be carried out, for example, by reacting the above epoxy resin (A) and an unsaturated monocarboxylic acid or a derivative thereof (B) in the presence of an esterification reaction catalyst at a temperature ranging from 100 to 150 ° C to form a polycarboxylate. The acid anhydride (C) is added to the reaction system and reacted at a temperature ranging from 90 to 120 ° C. Further, the production of the epoxy resin (A) and the production of the acid group-containing (meth) acrylate resin may be continuously performed.

The reaction ratio of the epoxy resin (A) to the unsaturated monocarboxylic acid or the derivative (B) thereof is 0.9 to 1.1 mol per 1 mol of the epoxy group in the epoxy resin (A). A range of unsaturated monocarboxylic acids or derivatives thereof (B) is preferred. Further, the reaction ratio of the polycarboxylic acid anhydride (C) is preferably from 0.2 to 1.0 mol per 1 mol of the epoxy group in the epoxy resin (A).

The esterification catalyst may be the same as those used in the reaction of the above polycarboxylic acid or its derivative (a1) and the raw material epoxy resin (a2). The amount of the catalyst added is preferably in the range of 0.03 to 5% by mass based on the total mass of the reaction raw materials.

The reaction can be carried out in an organic solvent as needed. The organic solvent to be used may, for example, be the same compound as that used in the reaction of the above polycarboxylic acid or its derivative (a1) and the raw material epoxy resin (a2). The amount of the organic solvent to be used is preferably from about 0.1 to 5 times the total mass of the reaction raw materials in terms of the reaction efficiency.

The acid value of the acid group-containing (meth) acrylate resin of the present invention is an acid group-containing (meth) acrylate resin which is excellent in developability in addition to the elongation or heat resistance of the cured product. It is preferably in the range of 40 to 90 mgKOH/g. Further, in the present invention, the acid value of the acid group-containing (meth) acrylate resin is a value measured by a titration method in accordance with JIS K 0070 (1992).

The acid group-containing (meth) acrylate resin of the present invention may be composed of a polymerizable (meth) acrylonitrile group in a molecular structure, for example, by adding a photopolymerization initiator as a curable resin. Use of materials.

The photopolymerization initiator may be appropriately selected depending on the type of the active energy ray to be irradiated or the like. Further, it may be used in combination with an optical sensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound or a nitrile compound. Specific examples of the photopolymerization initiator include, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- An alkylphenyl ketone photopolymerization initiator such as phenyl)phenyl]-1-butanone; a mercaptophosphine such as 2,4,6-trimethylbenzylindenyl-diphenyl-phosphine oxide An oxide-based photopolymerization initiator; an intramolecular hydrogen-attracting photopolymerization initiator such as a diphenyl ketone compound. These may be used alone or in combination of two or more.

The commercially available product of the photopolymerization initiator is, for example, "IRGACURE127", "IRGACURE184", "IRGACURE250", "IRGACURE270", "IRGACURE290", "IRGACURE369E", "IRGACURE379EG", "IRGACURE500", manufactured by BASF Corporation. "IRGACURE651", "IRGACURE754", "IRGACURE819", "IRGACURE907", "IRGACURE1173", "IRGACURE2959", "IRGACURE MBF", "IRGACURE TPO", "IRGACURE OXE 01", "IRGACURE OXE 02", manufactured by IGM RESINS "OMNIRAD184", "OMNIRAD250", "OMNIRAD369", "OMNIRAD369E", "OMNIRAD651", "OMNIRAD907FF", "OMNIRAD1173", etc.

The amount of the photopolymerization initiator to be added is preferably in the range of 0.05 to 15% by mass, more preferably in the range of 0.1 to 10% by mass, based on the total of the components other than the solvent of the curable resin composition. .

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 may, for example, be an epoxy resin such as a bisphenol epoxy resin or a novolak epoxy resin, and may be reacted with (meth)acrylic acid, a dicarboxylic anhydride, or an optionally unsaturated monocarboxylic anhydride. The obtained resin has a carboxyl group and a (meth)acryl oxime group resin, or various (meth) acrylate monomers.

Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (methyl). An aliphatic mono(meth)acrylate compound such as amyl acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or octyl (meth) acrylate, (meth) acrylate ring An alicyclic mono(meth)acrylate compound such as hexyl ester, isodecyl (meth)acrylate or adamantyl mono(meth)acrylate, glycidyl (meth)acrylate or tetrahydrofurfuryl acrylate And other heterocyclic mono(meth)acrylate compounds, benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, ( Phenyloxyethyl methacrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate a mono(meth)acrylate compound such as an aromatic mono(meth)acrylate compound such as an ester, benzylbenzyl (meth)acrylate or phenylphenoxyethyl (meth)acrylate; a polyoxyalkylene group in which a (poly)oxyethylidene chain, a (poly)oxypropylidene chain, a (poly)oxytetramethylene chain or the like is introduced into a molecular structure of various mono(meth)acrylate monomers. a chain (poly)oxyalkylene modified mono(meth)acrylate compound; a lactone modified single (in) lactone structure introduced into the molecular structure of the various mono(meth)acrylate compounds described above ( Methyl) acrylate compound; ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, new An aliphatic di(meth)acrylate compound such as pentanediol di(meth)acrylate; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate An alicyclic di(meth)acrylic acid such as norbornane dimethanol di(meth)acrylate, dicyclopentyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate or the like An ester compound; an aromatic di(meth)acrylate compound such as biphenol di(meth)acrylate or bisphenol di(meth)acrylate; and various di(meth)acrylates described above The polyoxyalkylene group of (poly)oxyalkylene chain, (poly)oxyalkylene chain, (poly)oxyalkylene chain, etc. a bis(meth) acrylate compound; a lactone-modified di(meth) acrylate compound having a (poly) lactone structure introduced into the molecular structure of the above various di(meth) acrylate compounds; An aliphatic tri(meth)acrylate compound such as a propane tri(meth)acrylate or a tris(meth)acrylate; introduced in the molecular structure of the aforementioned aliphatic tri(meth)acrylate compound (poly a (poly)oxyalkylene-modified tris(methyl) group of (poly)oxyalkylene chain, such as an oxygen-extended ethyl chain, a (poly)oxypropion propyl chain, a (poly)oxytetramethylene chain, or the like. An acrylate compound; a lactone-modified tri(meth) acrylate compound having a (poly) lactone structure introduced into the molecular structure of the aforementioned aliphatic tri(meth) acrylate compound; neopentyl alcohol tetra(methyl) A tetrafunctional or higher aliphatic poly(meth)acrylate of acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate Introducing (poly)oxyethylidene chain, (poly)oxypropionyl propyl chain, (poly)oxytetramethylene chain, etc. in the molecular structure of the aforementioned aliphatic poly(meth) acrylate compound ( a poly (alkyl)-modified (poly)oxyalkyl-modified poly(meth) acrylate compound having a polyalkylene alkyl chain; introduced (poly) in the molecular structure of the aforementioned aliphatic poly(meth) acrylate compound A tetrafunctional or higher lactone modified poly(meth) acrylate compound or the like of a lactone structure.

The curable resin composition of the present invention may contain an organic solvent for the purpose of adjusting the coating viscosity and the like. The type or amount of addition can be appropriately adjusted depending on the desired properties. In general, it is used in the range of 10 to 90% by mass based on the total amount of the curable resin composition. Specific examples of the solvent include, for example, a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; a cyclic ether solvent such as tetrahydrofuran or dioxolane; and methyl acetate. An ester of ethyl acetate or butyl acetate; an aromatic solvent such as toluene or xylene; an alicyclic solvent such as cyclohexane or methylcyclohexane; carbitol, sirlofur, methanol, and isopropanol. An alcohol solvent such as butanol or propylene glycol monomethyl ether; an alkylene glycol monoalkyl ether, a dialkyl alkyl glycol monoalkyl ether, a dialkyl alkyl glycol monoalkyl ether acetate, etc. A glycol ether solvent. These may be used alone or in combination of two or more.

The curable resin composition of the present invention may contain various additives such as inorganic fine particles or polymer fine particles, a pigment, an antifoaming agent, a viscosity adjusting agent, a leveling agent, a flame retardant, and a storage stabilizer. .

The acid group-containing (meth) acrylate resin of the present invention has a characteristic that the balance between the elongation of the cured product and the heat resistance is excellent. In general, in order to increase the elongation of the cured product, it is necessary to introduce a soft structure into the resin structure. However, in this case, the heat resistance of the cured product tends to be remarkably lowered. The acid group-containing (meth) acrylate resin of the present invention has a property of overturning the conventional technical knowledge from the viewpoint of simultaneously achieving such a high performance. The acid group-containing (meth) acrylate resin of the present invention can be used as a solder resist for applications in which the characteristics of the cured product are excellent in the balance between the elongation and the heat resistance of the cured product. A packaging adhesive layer of an interlayer insulating material, a packaging material, an underfill material, a circuit component, or the like is used as an adhesive layer between the circuit component and the circuit substrate. In addition, it can be applied to thin film transistor protective film, liquid crystal color filter protective film, color filter pigment resist, and black matrix resist for applications related to thin displays such as LCD and OELD. , spacer layer, etc.

Further, the acid group-containing (meth) acrylate resin of the present invention is excellent in developability in addition to the elongation and heat resistance of the cured product, and can be suitably used for solder resist applications. The resin material for solder resist of the present invention contains, for example, a curing agent, a curing accelerator, and an organic solvent in addition to the acid group-containing (meth) acrylate resin, the photopolymerization initiator, and various additives. Made.

The curing agent is not particularly limited as long as it has a functional group capable of reacting with a carboxyl group in the acid group-containing (meth) acrylate resin, and examples thereof include an epoxy resin. Examples of the epoxy resin used herein include a bisphenol epoxy resin, a phenyl ether epoxy resin, a naphthyl ether epoxy resin, a biphenyl epoxy resin, and a triphenylmethane ring. Oxygen resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol cophenolic varnish type epoxy resin , naphthol-cresol co-volum type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, and the like. These may be used alone or in combination of two or more. Among these epoxy resins, a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, a bisphenol novolac type epoxy resin, a naphthol novolac type varnish is excellent in heat resistance of a cured product. A novolac type epoxy resin such as an epoxy resin, a naphthol-phenol co-phenolic varnish type epoxy resin, a naphthol-cresol co-retort phenol resin type epoxy resin, and a softening point of 50 to 120 The range of °C is particularly good.

The curing accelerator is used to promote the curing reaction of the curing agent. When an epoxy resin is used as the curing agent, a phosphorus compound, a tertiary amine, an imidazole, an organic acid metal salt, a Lewis acid, an amine salt or the like may be mentioned. . These may be used alone or in combination of two or more. The amount of the hardening accelerator added is, for example, 1 to 10 parts by mass based on 100 parts by mass of the above-mentioned curing agent.

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

In the method of using the resin material for solder resist welding of the present invention to obtain a solder resist member, for example, the resin material for solder resist is applied onto a substrate, and the organic solvent is volatilized and dried at a temperature of about 60 to 100 ° C. Exposure is carried out by a mask which forms a desired pattern by ultraviolet rays or electron beams, and the unexposed portion is developed with an aqueous alkali solution, and further heated and hardened at a temperature of about 140 to 180 °C.

 [Examples]  

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

In the examples of the present invention, the acid value of the acid group-containing (meth) acrylate resin is measured by the neutralization titration method of JIS K 0070 (1992).

 Production Example 1 Production of Epoxy Resin (A-1)  

376 g of a bisphenol A type epoxy resin ("EPICLON 850S" manufactured by DIC Co., Ltd., epoxy equivalent: 188 g/eq), 6.6 g of bisphenol A, and a four-necked flask equipped with a thermometer, a stirrer, and a condenser were placed. 0.08 g of tetrabutylphosphonium bromide ("TBP-BB" manufactured by Behind Chemical Industry Co., Ltd.) was heated to 150 ° C for 2 hours. Then, 58 g of toluene diisocyanate ("TDI-80" manufactured by Mitsui Chemicals Co., Ltd.) was dropped under the same temperature for 3 hours. After the completion of the dropwise addition, the heating and stirring were continued, and the IR measurement was performed by sampling over time, and it was confirmed that the absorption peak of the isocyanate group (near 2250 to 2280 cm ^-1 ) disappeared, and 431 g of the molecule was obtained. An epoxy resin (A-1) having an oxazolidinone ring structure. The obtained epoxy resin (A-1) had an epoxy equivalent of 338 g/eq., and the softening point measured according to JIS K7234 was 79 ° C. According to ASTM D4287, the melt viscosity at 150 ° C measured by an ICI viscometer 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 and 300 g of DIC Co., Ltd. "EPICLON HP-7200L" (dicyclopentadiene) were added. Polyepoxypropyl ether of a phenol resin, an epoxy equivalent of 248 g/eq., 300 g of "DIC® N-695" manufactured by DIC Co., Ltd. (cresol novolac type epoxy resin, epoxy equivalent 215 g/equivalent) And 41 g of 1,4-cyclohexanedicarboxylic acid, 1.6 g of dibutylhydroxytoluene, and 1.9 g of triphenylphosphine were dissolved, and then reacted at 120 ° C for 3 hours under a nitrogen atmosphere. 0.4 g of methoquinone, 45 g of acrylic acid, and 0.5 g of triphenylphosphine were added, and the mixture was blown in air while reacting at 120 ° C for 15 hours. Further, 345 g of diethylene glycol monomethyl ether acetate and 217 g of tetrahydrofurfuric anhydride were added and reacted at 110 ° C for 5 hours to obtain an acid group-containing (meth) acrylate resin (1). Solution. The acid value of the solid content of the acid group-containing (meth) acrylate resin (1) was 80 mgKOH/g. The GPC chart of the acid group-containing (meth) acrylate resin (1) is shown in Fig. 1.

 Example 2 Manufacture 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 and 300 g of DIC Co., Ltd. "EPICLON HP-7200L" (dicyclopentadiene) were added. Polyepoxypropyl ether of a phenol resin, an epoxy equivalent of 248 g/eq., 300 g of "DIC® N-695" manufactured by DIC Co., Ltd. (cresol novolac type epoxy resin, epoxy equivalent 215 g/equivalent) And 41 g of 1,4-cyclohexanedicarboxylic acid, 1.6 g of dibutylhydroxytoluene, and 1.9 g of triphenylphosphine were dissolved, and then reacted at 120 ° C for 3 hours under a nitrogen atmosphere. 0.4 g of p-hydroxyanisole, 45 g of acrylic acid, and 0.5 g of triphenylphosphine were added, and the mixture was blown in air while reacting at 120 ° C for 15 hours. Further, 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 solution of the acid group-containing (meth) acrylate resin (2). . The acid value of the solid content of the acid group-containing (meth) acrylate resin (2) was 80 mgKOH/g.

 Example 3 Production of acid group-containing (meth) acrylate resin (3)  

334 g of diethylene glycol monomethyl ether acetate and 369 g of DIC Co., Ltd. "EPICLON HP-7200L" (dicyclopentadiene) were placed in a flask equipped with a thermometer, a stirrer, and a reflux condenser. Polyepoxypropyl ether of a molded phenol resin, epoxy equivalent: 248 g/eq.), 369 g of the epoxy resin (A-1) obtained in Production Example 1, and 41 g of 1,4-cyclohexanedicarboxylic acid After dissolving 1.9 g of dibutylhydroxytoluene and 2.3 g of triphenylphosphine, the mixture was reacted at 120 ° C for 3 hours under a nitrogen atmosphere. 0.5 g of p-hydroxyanisole, 152 g of acrylic acid, and 0.5 g of triphenylphosphine were added, and the mixture was blown in air while reacting at 120 ° C for 10 hours. Further, 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 an acid group-containing (meth) acrylate resin (2). ) solution. The acid value of the solid content of the acid group-containing (meth) acrylate resin (3) was 80 mgKOH/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 and 428 g of "DIC® N-680" manufactured by DIC Co., Ltd. (cresol novolac type ring) were added. An oxygen resin, an epoxy equivalent of 214 g/eq., 4 g of dibutylhydroxytoluene, and 0.4 g of p-hydroxyanisole were dissolved. Further, 144 g of acrylic acid and 1.6 g of triphenylphosphine were further added, and air was blown in while the esterification reaction was carried out at 120 ° C for 10 hours. Then, 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 acid value of the solid content of the acid group-containing (meth) acrylate resin (1') was 54.4 mgKOH/g.

 Examples 4 to 6 and Comparative Example 1  

The curable resin composition was prepared in the following manner, and various evaluation tests were carried out. The results are shown in Table 1.

 ◆Evaluation of heat resistance and elongation of hardened materials    ‧ Modulation of hardened resin composition  

100 g of the previously obtained acid group-containing (meth) acrylate resin, 24 g of DIC Co., Ltd. "EPICLON N-680" (cresol novolac type epoxy resin), and 5 g of BASF Corporation" Irgacure 907"[2-methyl-1-(4-methylthiophenyl)-2- Polinylpropan-1-one], 13 g of diethylene glycol monomethyl ether acetate, to obtain a curable resin composition.

 ‧hardened material  

The curable resin composition was coated on a glass substrate with a 50 μm coater, and dried at 80 ° C for 30 minutes. After irradiating ultraviolet rays of 1000 mJ/cm ² with a metal halide lamp, the mixture was heated at 160 ° C for 1 hour to peel off the cured product from the glass substrate to obtain a cured product.

 ‧ Evaluation of heat resistance of hardened materials  

A test piece of 6 mm × 40 mm was cut out from the cured product, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "RSAII" manufactured by Rheometric Co., Ltd., stretching method: frequency 1 Hz, temperature rising rate 3 ° C / minute) was used, and the elastic modulus was used. The temperature at which the change became maximum (the maximum rate of change of tan δ) was taken as the glass transition temperature (Tg), and the heat resistance was evaluated in accordance with the following criteria.

A: Glass transition temperature (Tg) is 130 ° C or higher

B: glass transition temperature (Tg) is less than 130 ° C

 ‧Evaluation of the elongation of hardened materials  

A test piece of 10 mm × 80 mm was cut out from the cured product, and the elongation was measured and evaluated under the following conditions using a tensile tester ("Conditional Universal Tester Autograph AG-IS" manufactured by Shimadzu Corporation).

Temperature 23 ° C, humidity 50%, distance between marking lines 20mm, distance between fulcrums 20mm, stretching speed 10mm / minute

A: elongation is 3.5% or more

B: elongation is 3% or more and less than 3.5%

C: elongation is less than 3%

 ◆Evaluation of light sensitivity    ‧ Modulation of hardened resin composition  

100g of the previously obtained acid group-containing (meth) acrylate resin, 24g of DIC Co., Ltd. "EPICLON N-680" (cresol novolac type epoxy resin), 10g of East Asia Synthetic Co., Ltd. "Lumicure DPA-600T" manufactured by the company (a composition containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in a molar ratio of 40/60) and "Irgacure 907" manufactured by BASF Co., Ltd. [2] -methyl-1-(4-methylthiophenyl)-2- Silyl propane-1-one], 13 g of diethylene glycol monomethyl ether acetate, and 0.65 g of indocyanine green as a pigment were kneaded by a roll mill to obtain a curable resin composition.

 ‧Measurement of light sensitivity  

The curable resin composition was coated on a glass substrate with a 50 μm coater, and dried at 80 ° C for 30 minutes. Then, using a metal halide lamp, a UV lamp of 500 mJ/cm ^{2 was} irradiated through a Step Tablet No. 2 manufactured by Kodak Co., Ltd. This was developed with a 1% by mass aqueous solution of sodium carbonate for 180 seconds, and the number of remaining stages was evaluated. The more residual levels, the higher the light sensitivity.

Claims (10)

 An acid group-containing (meth) acrylate resin containing an epoxy resin (A), an unsaturated monocarboxylic acid or a derivative thereof (B), and a polycarboxylic acid anhydride (C) as essential reaction materials An acid-based (meth) acrylate resin in which the epoxy resin (A) has an ester bond site derived from a polycarboxylic acid or a derivative (a1) in a molecular structure.    An acid group-containing (meth) acrylate resin according to claim 1, wherein the epoxy resin (A) is an essential reaction of the polycarboxylic acid or a derivative thereof (a1) and a raw material epoxy resin (a2). raw material.    The acid group-containing (meth) acrylate resin of claim 2, wherein a plurality of epoxy resins are used in the raw material epoxy resin (a2).   The (meth) acrylate resin containing an acid group according to claim 2, wherein, in the case of the raw material epoxy resin (a2), one to a plurality of compounds (P) containing a phenolic hydroxyl group, and a structure A polyepoxypropyl ether (raw material epoxy resin (a2-2)) which is a reaction product of the compound (y) represented by any one of the formulas (y-1) to (y-5) as an essential reaction raw material , wherein the structural formula (y-1)~(y-5) is as follows: [Wherein h is 0 or 1; R & lt independently ^1, an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, an aralkyl group of any one of; I is an integer of 0 or 1 to 4, ; Z is any one of a vinyl group, a halomethyl group, a methylol group, or an alkoxymethyl group; Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom or a carbonyl group; An integer from 1 to 4].  The acid group-containing (meth) acrylate resin of 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 containing the acid group-containing (meth) acrylate resin according to any one of claims 1 to 5, and a photopolymerization initiator.    A cured product which is a cured product of the curable resin composition of claim 6.    An insulating material comprising the curable resin composition of claim 6.    A resin material for solder resist, comprising the curable resin composition of claim 6.    A solder resist member comprising the resin material for solder resist as claimed in claim 9.