WO2018173679A1 - 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

Acid group-containing (meth) acrylate resin and solder resist resin material

The present invention provides 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 resin, an insulating material comprising the curable resin composition, and a solder resist 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 after an epoxy resin is acrylated with acrylic acid is widely used. The required performance for the resin material for solder resist includes various properties such as curing with a small exposure amount, excellent alkali developability, and excellent heat resistance, strength, flexibility, dielectric properties, etc. in the cured product.

As a conventionally known resin material for solder resist, an acid obtained by further reacting a reaction product of cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin and bisphenol F with acrylic acid and tetrahydrophthalic anhydride. 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 has characteristics that are 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 easily cracked and has poor reliability. There existed problems, such as not being suitable for the use for which a softness | flexibility is calculated | required, such as a flexible substrate.

Special table 2012-503690 gazette

Therefore, the problem to be solved by the present invention is 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 acid group, and the curable resin composition. An insulating material, a resin material for solder resist, and a resist member are provided.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an ester bond site derived from a polycarboxylic acid or a derivative thereof has a molecular structure as an epoxy resin that is a reaction raw material of an acid group-containing epoxy (meth) acrylate resin. By using what is contained therein, it has been found that the resin material has an excellent balance between elongation and heat resistance in a cured product while maintaining performance such as photosensitivity and alkali developability, and the present invention has been completed. It was.

That is, the present invention is an acid group-containing (meth) acrylate resin comprising an epoxy resin (A), an unsaturated monocarboxylic acid or derivative thereof (B), and a polycarboxylic acid anhydride (C) as essential reaction raw materials. The epoxy resin (A) relates to an acid group-containing (meth) acrylate resin having an ester bond site derived from a polycarboxylic acid or a derivative thereof (a1) in the 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 solder resist resin material comprising the curable resin composition.

The present invention further relates to a resist member made of 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 resin, an insulating material comprising the curable resin composition, and a solder A resist resin material and a resist member can be provided.

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

Hereinafter, the present invention will be described in detail.
The acid group-containing (meth) acrylate resin of the present invention comprises an epoxy resin (A), an unsaturated monocarboxylic acid or derivative thereof (B), and a polycarboxylic acid anhydride (C) as essential reaction materials, and the epoxy resin. (A) has an ester bond site derived from polycarboxylic acid or its derivative (a1) in the 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. The (meth) acryloyl group means one or both of an acryloyl group and a methacryloyl group, and (meth) acrylate is a general term for acrylate and methacrylate.

The epoxy resin (A) is characterized by having an ester bond site derived from polycarboxylic acid or its derivative (a1) in the molecular structure. This feature is an essential requirement for obtaining an acid group-containing (meth) acrylate resin that has an excellent balance between elongation and heat resistance in the cured product. The epoxy resin (A) is not limited as long as it has an ester bond site derived from polycarboxylic acid or its derivative (a1) in the molecular structure and has a plurality of epoxy groups in the molecular structure. The structure is not particularly limited, and any structure may be used. As an example of the said epoxy resin (A), the epoxy resin obtained by using the said polycarboxylic acid or its derivative (a1) and 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, acid halides, acid anhydrides and the like thereof. 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 cross-linking agent by an ester bond. Compounds can be used. The number and type of the carboxy group-derived functional group of the polycarboxylic acid or its derivative (a1) is appropriately selected according to the reactivity with the raw material epoxy resin (a2), the desired cured product performance, and the like. Especially, since it becomes acid group containing (meth) acrylate resin which is further excellent in the balance of the elongation and heat resistance in hardened | cured material, the dicarboxylic acid compound which has two carboxy groups is preferable. Specific examples of the dicarboxylic acid compound include compounds represented by the following structural formula (1).

(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. It is a structured part.)

Referring to 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 the acid group-containing (meth) acrylate resin is further excellent in the balance between elongation and heat resistance in the cured product. Examples of the alicyclic structure of the alicyclic structure-containing hydrocarbon group include a cyclopentane structure, a cyclohexane structure, a norbornane structure, a norbornene structure, a tricyclodecane structure, a dicyclopentadiene structure, and an adamantane structure. As long as the alicyclic structure-containing hydrocarbon group has one or more of these alicyclic structures, an aliphatic hydrocarbon group as a bonding group between the alicyclic structures or a bonding group between the alicyclic structure and the carboxy group. Etc. may be contained. The aliphatic hydrocarbon group as the linking group is preferably an alkylene group having 1 to 6 carbon atoms. Examples of the aromatic ring structure possessed by the aromatic ring-containing hydrocarbon group include a benzene ring, a naphthalene ring, and an anthracene ring. 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 bonding group between aromatic rings or a bonding group between an alicyclic ring and a carboxy group. You may do it. The aliphatic hydrocarbon group as the linking group is preferably an alkylene group having 1 to 6 carbon atoms. Examples of the alkoxy group include alkoxy groups 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 site in which one or more of hydrogen atoms on the aromatic nucleus are substituted with an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, or the like. It is done. Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.

Among the dicarboxylic acid compounds, an acid group-containing (meth) acrylate resin having a further excellent balance between elongation and heat resistance in a cured product is obtained, and therefore X in the structural formula (1) is an alicyclic structure-containing hydrocarbon. A group or a structure site in which one or more hydrogen atoms in the alicyclic structure-containing hydrocarbon group are substituted with an alkoxy group, an aryloxy group, a halogen atom or the like is preferable. Furthermore, what has a cyclohexane structure as an alicyclic structure is more preferable.

The raw material epoxy resin (a2) is not particularly limited as long as it is a resin having a plurality of epoxy groups, and a wide variety of materials can be used. Especially, since it becomes acid group containing (meth) acrylate resin with especially high heat resistance in hardened | cured material, what has an aromatic ring in a resin structure is preferable. One example is polyglycidyl ether of phenolic hydroxyl group-containing resin. More specifically, for example, a polyglycidyl ether of a novolak type resin (hereinafter referred to as “raw material epoxy resin (a2-1)”) using one or more phenolic hydroxyl group-containing compounds (P) as a reaction raw material, A reaction product comprising one or more phenolic hydroxyl group-containing compounds (P) and a compound (y) represented by any one of the following structural formulas (y-1) to (y-5) as essential reaction raw materials And polyglycidyl ether (hereinafter referred to as “raw material epoxy resin (a2-2)”).

[In the formula, 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 one of a vinyl group, a halomethyl group, a hydroxymethyl group, and an alkyloxymethyl group. Y is any one 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) includes, for example, phenol, polyhydroxybenzene, naphthol, polyhydroxynaphthalene, anthracenol, polyhydroxyanthracene, biphenol, bisphenol, and one or more of these on the aromatic nucleus. Examples thereof include compounds having a substituent. 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, and an aralkyl group. The aliphatic hydrocarbon group may be either linear or branched, and may have an unsaturated bond in the structure. Specific examples 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, and a nonyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy 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 anthryl group, and a structural site in which the aromatic hydrocarbon group, the alkoxy group, the halogen atom, or the like is substituted on the aromatic nucleus. Examples of the aryloxy group include a phenyloxy group, a naphthyloxy group, an anthryloxy group, and a structural site in which the alkyl group, alkoxy group, halogen atom, or the like is substituted on the aromatic nucleus. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and a structural site in which the alkyl group, alkoxy group, halogen atom, or the like is substituted on the aromatic nucleus. The phenolic hydroxyl group-containing compound (P) may be used singly or in combination of two or more. Among them, since it becomes an acid group-containing (meth) acrylate resin having excellent developability in addition to elongation and heat resistance in the cured product, a compound having one or more substituents on the aromatic nucleus of phenol or phenol Preferable is phenol or alkylphenol having one or more alkyl groups having 1 to 6 carbon atoms.

In 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 the acid group-containing (meth) acrylate resin is further excellent in the balance between elongation and heat resistance in the cured product.

The novolac resin using the phenolic hydroxyl group-containing compound (P) as a reaction raw material can be produced by the same production method as a general novolac resin. The molecular weight and the like of the novolac resin 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 between the phenolic hydroxyl group-containing compound (P) and the compound (y) can be carried out by a method of heating and stirring under acid catalyst conditions and at a temperature of about 70 to 180 ° C. The reaction ratio between the phenolic hydroxyl group-containing compound (P) and the compound (y) is such that the phenolic hydroxyl group-containing compound (P) is 1.5 to 5 moles per mole of the compound (y). It is preferable that

The polyglycidyl etherification reaction of the phenolic hydroxyl group-containing resin can be performed by a known and conventional method. As an example, for example, 2 to 10 mol of epihalohydrin is used with respect to 1 mol of phenolic hydroxyl group contained in the phenolic hydroxyl group-containing resin, and 0.9 to 2.0 mol of basicity with respect to 1 mol of phenolic hydroxyl group. Examples thereof include a method of reacting at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while adding the catalyst all at once or dividedly.

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

The raw material epoxy resin (a2) may be used alone or in combination of two or more. Among these, the raw material epoxy resin (a2-2) is preferably used as an essential component because the acid group-containing (meth) acrylate resin is further excellent in the balance of elongation and heat resistance in the cured product. Furthermore, in the obtained acid group-containing (meth) acrylate resin, in addition to the elongation and heat resistance in the cured product, various performances can be imparted, and balance control of each performance becomes easy. It is preferable to use a plurality of types of epoxy resins 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 weight of the raw material epoxy resin (a2) is preferably 30% by mass or more, more preferably in the range of 30 to 80% by mass, and 40 to 70%. It is particularly preferable that the mass range. Further, the total mass of the raw material epoxy resin (a2-1) and the raw material epoxy resin (a2-2) with respect to the total mass of the raw material epoxy resin (a2) is preferably 50% by mass or more, and 80% by mass. More preferably.

When two or more kinds are used together as the raw material epoxy resin (a2), the raw material epoxy resin (a2) produced separately may be used, or it may be used at the stage of the phenolic hydroxyl group-containing resin to be polyglycidyl etherified. You may use what you did.

The reaction between the polycarboxylic acid or its derivative (a1) and the raw material epoxy resin (a2) can be performed, 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 that is excellent in developability in addition to elongation and heat resistance in the cured product. From the above, it is preferable to use the polycarboxylic acid or its derivative (a1) in the range of 0.5 to 20% by mass, and in the range of 1 to 10% by mass, based on the total mass of the raw material epoxy resin (a2). It is more preferable.

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 amount of the catalyst added is preferably in the range of 0.05 to 5% by mass with respect to the total mass of the polycarboxylic acid or derivative (a1) and the raw material epoxy resin (a2).

The reaction between the polycarboxylic acid or its derivative (a1) and the raw material epoxy resin (a2) may be performed in an organic solvent as necessary. The organic solvent to be used is appropriately selected depending on the solubility of the acid group-containing (meth) acrylate resin that is the reaction raw material and the product and the reaction temperature conditions. For example, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, Examples include methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate and the like. These may be used alone or as a mixed solvent 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 raw materials because the reaction efficiency is good.

Further, as the epoxy resin (A), an epoxy resin having an oxazolidone ring structure in the molecular structure can also be used.

The epoxy resin having an oxazolidone ring structure in the molecular structure is not particularly limited as long as it has an oxazolidone ring structure in the molecular structure, and various kinds of resins can be used. . As an example of the epoxy resin having an oxazolidone ring structure in the molecular structure, for example, the polyglycidyl etherified product of the phenolic hydroxyl group-containing compound (P) described above and the polyisocyanate compound (a3) are used as essential reaction raw materials. Reaction products are mentioned.

As long as the polyisocyanate compound (a3) is a compound having a plurality of isocyanate groups in the molecule, the specific structure and the presence or absence of other functional groups are not particularly limited, and various types 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; aromas such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate Group diisocyanate compound; 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.

[Wherein, R ¹ is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ² is each independently an alkyl group having 1 to 4 carbon atoms or a bonding point linked to a structural moiety represented by the structural formula (2) via a methylene group marked with *. m is 0 or an integer of 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, acid halides, acid anhydrides thereof, and the like. It is done. These may be used alone or in combination of two or more.

As the polycarboxylic acid anhydride (C), any acid anhydride of a compound having two or more carboxy groups in one molecule can be used. 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, Examples thereof include acid anhydrides of dicarboxylic acid compounds such as hexahydrophthalic acid and methylhexahydrophthalic acid. Polycarboxylic acid anhydrides (C) may be used alone or in combination of two or more. Above all, in the point that it becomes an acid group-containing (meth) acrylate resin with excellent heat resistance in cured products, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, etc. An acid anhydride of a compound having a cyclic structure is preferred. Moreover, a succinic anhydride is preferable in that the acid group-containing (meth) acrylate resin is excellent in developability.

The acid group-containing (meth) acrylate resin of the present invention uses 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, either the method of reacting all the reaction raw materials collectively, or the method of reacting sequentially may be sufficient. Among them, since the reaction is easily controlled, the epoxy resin (A) is first reacted with the unsaturated monocarboxylic acid or derivative (B), and then the polycarboxylic acid anhydride (C) is reacted. The method is preferred. The reaction is performed, for example, by reacting the epoxy resin (A) with the unsaturated monocarboxylic acid or derivative (B) in the presence of an esterification reaction catalyst in a temperature range of 100 to 150 ° C. The polycarboxylic acid anhydride (C) can be added to the mixture and reacted in a temperature range of 90 to 120 ° C. Moreover, you may perform manufacture of the said epoxy resin (A), and manufacture of an acid group containing (meth) acrylate resin continuously.

The reaction ratio of the epoxy resin (A) to the unsaturated monocarboxylic acid or its derivative (B) is the ratio of the unsaturated monocarboxylic acid or its derivative (B) to 1 mol of the epoxy group in the epoxy resin (A). It is preferably used in the range of 0.9 to 1.1 mol. The reaction rate of the polycarboxylic acid anhydride (D) is preferably in the range of 0.2 to 1.0 mol with respect to 1 mol of the epoxy group in the 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). The addition amount of the catalyst is preferably in the range of 0.03 to 5% by mass with respect to the total mass of the reaction raw materials.

The reaction may be performed in an organic solvent as 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 raw materials because the reaction efficiency is good.

Since the acid value of the acid group-containing (meth) acrylate resin of the present invention is an acid group-containing (meth) acrylate resin that is excellent in developability in addition to elongation and heat resistance in the cured product, 40 to 90 mgKOH / g It is preferable that it is the range of these. In the present invention, the acid value of the acid group-containing (meth) acrylate resin is a value measured by a 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 can be used as a curable resin composition by adding a photopolymerization initiator. Can do.

The photopolymerization initiator may be selected and used according to the type of active energy ray to be irradiated. Moreover, you may use together with photosensitizers, such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, a nitrile compound. 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- Examples include acylphosphine oxide photopolymerization initiators such as phosphine oxide; intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds. These may be used alone or in combination of two or more.

Commercially available products of the photopolymerization initiator include, for example, “IRGACURE127”, “IRGACURE184”, “IRGACURE250”, “IRGACURE270”, “IRGACURE290”, “IRGACURE369E”, “IRGACURE379EG”, “IRGACURE500”, “IRGACURE500”, manufactured by BASF. , “IRGACURE 754”, “IRGACURE 819”, “IRGACURE 907”, “IRGACURE 1173”, “IRGACURE 2959”, “IRGACURE MBF”, “IRGACURE TPO”, “IRGACURE OXE 01”, “IRGACUREOX 4” , "OMNIRAD250", "OM IRAD369 "," OMNIRAD369E "," OMNIRAD651 "," OMNIRAD907FF "," OMNIRAD1173 ", and the like.

The addition amount of the photopolymerization initiator is preferably in the range of 0.05 to 15% by mass, for example, in the range of 0.1 to 10% by mass with respect to the total of components other than the solvent of the curable resin composition. 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 is obtained, for example, by reacting an epoxy resin such as a bisphenol type epoxy resin or a novolak type epoxy resin with (meth) acrylic acid, dicarboxylic acid anhydride, and unsaturated monocarboxylic acid anhydride as required. Examples thereof include resins having a carboxyl group and a (meth) acryloyl group in the resin, and various (meth) acrylate monomers.

Examples of the (meth) acrylate monomer include 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 meth) acrylate 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 (me ) Acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benzylbenzyl (meth) acrylate , Mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds such as phenylphenoxyethyl (meth) acrylate: (poly) oxyethylene chains in the molecular structure of the various mono (meth) acrylate monomers, (poly ) (Poly) oxyalkylene-modified mono (meth) acrylate compounds introduced with polyoxyalkylene chains such as oxypropylene chains and (poly) oxytetramethylene chains; the 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 Such as alicyclic di (meth) acrylate compounds; aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylate and bisphenol di (meth) acrylate; A polyoxyalkylene-modified di (meth) acrylate compound in which a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain is introduced into the molecular structure of the compound; A lactone-modified di (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of 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 compound introduced with (poly) oxyalkylene chain such as oxypropylene chain and (poly) oxytetramethylene chain; in the molecular structure of the aliphatic tri (meth) acrylate compound ( A lactone-modified tri (meth) acrylate compound having a poly) lactone structure;

Tetra- or higher functional aliphatic poly (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; (Poly) oxyalkylene-modified poly (meth) having 4 or more functionalities in which (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, or other (poly) oxyalkylene chain is introduced into the molecular structure Acrylate compounds; tetrafunctional or higher functional 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 the coating viscosity. The kind and addition amount are appropriately adjusted according to the desired performance. Generally, it is used in the range of 10 to 90% by mass with respect to the total of the curable resin composition. Specific examples of the solvent include, for example, 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; aromatics such as toluene and xylene. Solvents; cycloaliphatic, methylcyclohexane and other alicyclic solvents; carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether and other alcohol solvents; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol mono Examples include glycol ether solvents such as alkyl ether acetates. These may be used alone or in combination of two or more.

In addition to this, the curable resin composition of the present invention may contain various additives such as inorganic fine particles and polymer fine particles, pigments, antifoaming agents, viscosity modifiers, leveling agents, flame retardants, and storage stabilizers. .

The acid group-containing (meth) acrylate resin of the present invention is characterized by an excellent balance between elongation and heat resistance in a cured product. In general, in order to increase the elongation of a cured product, it is necessary to introduce a flexible structure into 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 defeats the conventional technical knowledge in that both of these difficult performances are combined at a high level. The acid group-containing (meth) acrylate resin of the present invention is used as an application in which the balance between elongation and heat resistance in a cured product is utilized, for example, as a semiconductor device-related application, a solder resist, an interlayer insulating material, It can be used as a package adhesive layer such as a package material, an underfill material or a circuit element, or an adhesive layer between an integrated circuit element and a circuit board. In addition, thin film display applications such as LCD and OELD can be suitably used for thin film transistor protective films, liquid crystal color filter protective films, color filter pigment resists, black matrix resists, spacers, and the like.

Moreover, since the acid group-containing (meth) acrylate resin of the present invention is excellent in developability as well as elongation and heat resistance in a cured product, it can be suitably used for solder resist applications. The resin material for solder resist of the present invention includes, for example, each component such as 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. Become.

The curing agent is not particularly limited as long as it has a functional group capable of reacting with a carboxy group in the acid group-containing (meth) acrylate resin, and examples thereof include an epoxy resin. Examples of the epoxy resin used here include 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, and cresol novolac type epoxy resin. Bisphenol novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol Examples include addition reaction type epoxy resins. These may be used alone or in combination of two or more. Among these epoxy resins, phenolic novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin because of excellent heat resistance in cured products. Novolak type epoxy resins such as naphthol-cresol co-condensed novolak 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. 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, Examples include amine complex salts. 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. For example, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, Examples include cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate.

The method of obtaining a resist member using the solder resist resin material of the present invention is, for example, by applying the solder resist resin material on a substrate and evaporating and drying the organic solvent in a temperature range of about 60 to 100 ° C. Thereafter, there is a method in which a non-exposed portion is exposed with an ultraviolet solution or an electron beam through a photomask having a desired pattern formed, and an unexposed portion is developed with an alkaline aqueous solution, and further heated and cured in a temperature range of about 140 to 180 ° C. .

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples.

In the examples of the present application, the acid value of the acid group-containing (meth) acrylate resin 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, stirrer, and condenser, 376 g of a bisphenol A type epoxy resin (“EPICLON 850S” epoxy equivalent of 188 g / equivalent) manufactured 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. and reacted for 2 hours. Subsequently, 58 g of tolylene diisocyanate (“TDI-80” manufactured by Mitsui Chemicals) was added dropwise under the same temperature condition over 3 hours. After completion of the dropwise addition, heating and stirring are continued, sampling with time and IR measurement are performed, and it is confirmed that the absorption peak of the isocyanate group (near 2250 to 2280 cm ⁻¹ ) has disappeared, so that the molecule has an oxazolidone ring structure. 431 g of epoxy resin (A-1) was obtained. The epoxy equivalent of the obtained epoxy resin (A-1) was 338 g / equivalent, the softening point measured according to JIS K7234 was 79 ° C., and the melt viscosity at 150 ° C. measured with an ICI viscometer in accordance with ASTM D4287 was 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-7200L” manufactured by DIC Corporation (di) 300 g of polyglycidyl ether of cyclopentadiene addition type phenolic resin, epoxy group equivalent 248 g / equivalent), “EPICLON N-695” (cresol novolak type epoxy resin, epoxy group equivalent 215 g / equivalent) manufactured by DIC Corporation, and 1,4- After adding and dissolving 41 g of cyclohexanedicarboxylic acid, 1.6 g of dibutylhydroxytoluene, and 1.9 g of triphenylphosphine, they were reacted at 120 ° C. for 3 hours in a nitrogen atmosphere. 0.4 g of methoquinone, 45 g of acrylic acid and 0.5 g of triphenylphosphine were added and reacted at 120 ° C. for 15 hours while blowing air. Furthermore, 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 the 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 mgKOH / 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-7200L” manufactured by DIC Corporation (di) 300 g of polyglycidyl ether of cyclopentadiene addition type phenolic resin, epoxy group equivalent 248 g / equivalent), “EPICLON N-695” (cresol novolak type epoxy resin, epoxy group equivalent 215 g / equivalent) manufactured by DIC Corporation, and 1,4- After adding and dissolving 41 g of cyclohexanedicarboxylic acid, 1.6 g of dibutylhydroxytoluene, and 1.9 g of triphenylphosphine, they were reacted at 120 ° C. for 3 hours in a nitrogen atmosphere. 0.4 g of methoquinone, 45 g of acrylic acid and 0.5 g of triphenylphosphine were added and reacted at 120 ° C. for 15 hours while blowing 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 the 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 mgKOH / 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-7200L” manufactured by DIC Corporation (di) 369 g of cyclopentadiene addition type phenolic resin, glycine ether (epoxy group equivalent 248 g / equivalent), 369 g of epoxy resin (A-1) obtained in Production Example 1, 41 g of 1,4-cyclohexanedicarboxylic acid, 1.9 g of dibutylhydroxytoluene Then, 2.3 g of triphenylphosphine was added and dissolved, and then reacted at 120 ° C. for 3 hours in a nitrogen atmosphere. 0.5 g of methoquinone, 152 g of acrylic acid and 0.5 g of triphenylphosphine were added and reacted at 120 ° C. for 10 hours while blowing 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 the 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 mgKOH / g.

Comparative Production Example 1 Production of Acid Group-Containing (Meth) acrylate Resin (1 ′) In a flask equipped with a thermometer, stirrer and 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, dibutylhydroxytoluene 4 g, and methoquinone 0.4 g were added and dissolved. Furthermore, 144 g of acrylic acid and 1.6 g of triphenylphosphine were added, and an esterification reaction was performed at 120 ° C. for 10 hours while blowing 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 mgKOH / g.

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

◆ Evaluation of heat resistance and elongation of cured product / Preparation of curable resin composition 100 g of acid group-containing (meth) acrylate resin obtained above, “EPICLON N-680” (cresol novolac type epoxy resin) manufactured by DIC Corporation 24 g, “Irgacure 907” [2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one] manufactured by BASF, and 13 g of diethylene glycol monomethyl ether acetate were blended to prepare a curable resin composition. Obtained.

-Preparation of hardened | cured material The curable resin composition was apply | coated with the 50 micrometer applicator on the glass base material, and was dried for 30 minutes at 80 degreeC. After irradiating with 1000 mJ / cm ² ultraviolet rays 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 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.), tension method: frequency 1 Hz, heating rate 3 (° C./min), the temperature at which the change in the elastic modulus is maximum (the tan δ change rate is the largest) is defined 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 higher B: Glass transition temperature (Tg) is lower than 130 ° C.

・ Evaluation of elongation of cured product A 10mm x 80mm test piece was cut out from the cured product, and the elongation was measured under the following conditions using a tensile tester ("Confidential Universal Tester Autograph AG-IS" manufactured by Shimadzu Corporation). And evaluated.
Temperature 23 ° C., humidity 50%, distance between marked lines 20 mm, distance between fulcrums 20 mm, pulling speed 10 mm / min A: elongation 3.5% or more B: elongation 3% or more and less than 3.5% C: elongation Less than 3%

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

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

Claims (10)

1. An acid group-containing (meth) acrylate resin containing an epoxy resin (A), an unsaturated monocarboxylic acid or derivative thereof (B), and a polycarboxylic acid anhydride (C) as essential reaction raw materials, An acid group-containing (meth) acrylate resin in which A) has an ester bond site derived from polycarboxylic acid or its derivative (a1) in the molecular structure.
2. The acid group-containing (meth) acrylate resin according to claim 1, wherein the epoxy resin (A) comprises the polycarboxylic acid or its derivative (a1) and the raw material epoxy resin (a2) as essential reaction raw materials.
3. 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).
4. As the raw material epoxy resin (a2), one or more phenolic hydroxyl group-containing compounds (P) and the following structural formulas (y-1) to (y-5)
   

   

   [In the formula, 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 one of a vinyl group, a halomethyl group, a hydroxymethyl group, and an alkyloxymethyl group. Y is any one 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 acid group-containing (meth) acrylate according to claim 2, wherein the reaction product polyglycidyl ether (raw material epoxy resin (a2-2)) is used as an essential reaction material. resin.
5. 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).
6. 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.
7. A cured product of the curable resin composition according to claim 6.
8. An insulating material comprising the curable resin composition according to claim 6.
9. A resin material for a solder resist comprising the curable resin composition according to claim 6.
10. A resist member comprising the resin material for solder resist according to claim 9.

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