TWI768019B - Acid group-containing (meth)acrylate resins and resin materials for solder resists - Google Patents

Abstract

The present invention provides an acid group-containing (meth)acrylate resin, which uses epoxy resin (A), unsaturated monocarboxylic acid or its derivative (B) and polycarboxylic acid anhydride (C) as necessary reaction raw materials , characterized in that the aforementioned epoxy resin (A) is the reaction product of the raw epoxy resin (a1) and the polyhydroxy compound (a2), wherein the raw epoxy resin (a1) is a bis(hydroxynaphthyl) alkane compound The polyglycidyl ether of (p1) is an essential component. The acid group-containing (meth)acrylate resin can form a cured product excellent in ductility and heat resistance.

Description

Acid group-containing (meth)acrylate resins and resin materials for solder resists

The present invention relates to an acid group-containing (meth)acrylate resin excellent in the balance between ductility and heat resistance in a cured product, a curable resin composition containing the same, an insulating material composed of the aforementioned curable resin composition, Resin material and photoresist member for solder resist.

The acid group-containing epoxy acrylate resin obtained by reacting an acid anhydride after acrylated epoxy resin with acrylic acid is widely used as a resin material for solder resists for printed wiring boards. The properties required for the solder resist resin material include: curing with a small amount of exposure, excellent alkali developability, excellent heat resistance, strength, flexibility, elongation, and dielectric properties of the cured product. performance.

As a conventional resin material for solder resists, an acid group-containing epoxy resin obtained by reacting 1,1-bis(2,7-glycidoxynaphthyl)methane with acrylic acid and tetrahydrophthalic anhydride is known. Acrylate resin (refer to the following patent document 1). The acid group-containing epoxy acrylate resin described in Patent Document 1 is characterized in that it is superior in heat resistance to the acid group-containing epoxy acrylate resin using a novolac type epoxy resin as a raw material, but the cured product has the characteristics of superior heat resistance. The ductility is very low, the cured product is prone to cracks, and the reliability is poor, so it is not suitable for applications requiring flexibility such as flexible substrates.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-89644

Therefore, the problem to be solved by the present invention is to provide an acid group-containing (meth)acrylate resin excellent in the balance between ductility and heat resistance in a cured product, a curable resin composition containing the same, and a curable resin composed of the above-mentioned curable resin. Insulation material, resin material for solder resist, and photoresist member composed of composition.

The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that a reaction product between a raw material epoxy resin and a polyhydroxy compound is used, which has polyglycidyl ether of a bis(hydroxynaphthyl)alkane compound as an essential component. Epoxy resin, which is a reaction raw material of epoxy (meth)acrylate resin containing acid group, maintains properties such as photosensitivity and alkali developability, and is a resin material excellent in the balance between ductility and heat resistance in the cured product , and then complete the present invention.

That is, the present invention relates to an acid group-containing (meth)acrylate resin comprising epoxy resin (A), unsaturated monocarboxylic acid or its derivative (B) and polycarboxylic acid anhydride (C) as Necessary reaction raw materials, wherein the aforementioned epoxy resin (A) is the reaction product of the raw epoxy resin (a1) and the polyhydroxy compound (a2), wherein the raw epoxy resin (a1) is made of bis(hydroxynaphthalene) (p1) polyglycidyl ether of the alkane compound (p1) as an essential component.

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

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

The present invention further relates to an insulating material composed of the aforementioned curable resin composition.

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

The present invention further relates to a photoresist member composed of the aforementioned resin material for solder resists.

According to the present invention, it is possible to provide an acid group-containing (meth)acrylate resin excellent in the balance between ductility and heat resistance in a cured product, a curable resin composition containing the same, and a curable resin composition composed of the above-mentioned curable resin composition. Insulation material, resin material for solder resist, and photoresist member.

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

[Form of implementing the invention]

The present invention will be explained in detail below.

The (meth)acrylate resin containing an acid group of the present invention is a kind of An acid group-containing (meth)acrylate resin containing an epoxy resin (A), an unsaturated monocarboxylic acid or its derivative (B), and a polycarboxylic acid anhydride (C) as necessary reaction raw materials, characterized in that the epoxy resin Resin (A) is a reaction product of raw material epoxy resin (a1) and polyhydroxy compound (a2), wherein the raw epoxy resin (a1) is a polyepoxy resin containing bis(hydroxynaphthyl)alkane compound (p1) propyl ether as an essential ingredient.

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

The epoxy resin (A) is a reaction product of the raw material epoxy resin (a1) and the polyhydroxy compound (a2), the polyglycidyl ether of the bis(hydroxynaphthyl)alkane compound (p1) being an essential component, This feature is an essential requirement for obtaining an acid group-containing (meth)acrylate resin excellent in the balance between ductility and heat resistance in a cured product.

As long as the above-mentioned bis(hydroxynaphthyl)alkane compound (p1) has a structure in which a naphthalene skeleton containing one to a plurality of hydroxyl groups is bound by an alkylene group, other specific structures are not particularly limited, and various kinds of compounds can be used. compound. One of the preferred specific examples includes a compound represented by the following structural formula (1).

[In the formula, R ¹ is each independently any one of an aliphatic hydrocarbon group, an alkoxy group, and a halogen atom, R ² is an alkylene group, k is 1 or 2, and l is 0 or an integer from 1 to 6. ]

The bis(hydroxynaphthyl)alkane compound (p1) may be used alone or in combination of two or more.

Regarding R ¹ in the aforementioned structural formula (1), the aforementioned aliphatic hydrocarbon group may be of a straight-chain type or a branched type, and may have one to plural unsaturated bonds. Also, the number of carbon atoms is not particularly limited. Among them, an alkyl group having 1 to 6 carbon atoms is preferable from the viewpoint of being an acid group-containing (meth)acrylate resin having a more excellent balance of ductility and heat resistance in the cured product. Examples of the alkoxy group include alkoxy groups having about 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group. As said halogen atom system, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

Regarding R ² in the aforementioned structural formula (1), the number of carbon atoms of the alkylene group is not particularly limited. Among them, an alkylene group having 1 to 6 carbon atoms is preferable, and a carbon An alkylene group having 1 to 3 atoms.

Regarding the hydroxyl group in the aforementioned structural formula (1), k is 1 or 2, and two k may be the same number or different from each other. When k is 1, the substitution position of the hydroxyl group is preferably the 2nd position with respect to the carbon atom to which R ² is bonded. In addition, when k is 2, the substitution positions of the hydroxyl group are preferably the 2nd and 7th positions with respect to the carbon atom to which R ² is bonded. Therefore, as a more preferable compound among the said compound (a1), the compound represented by any one of following structural formula (1-1) to (1-3) is mentioned.

[In the formula, R ¹ is each independently any one of aliphatic hydrocarbon group, alkoxy group, halogen atom, R ² is alkylene group, l is 0 or an integer of 1 to 6, m is 0 or 1 to 5 Integer. ]

The said raw material epoxy resin (a1) may contain other components other than the polyglycidyl ether of the said compound (p1). Among other components, polyglycidyl ether of the compound (p2) represented by the following structural formula (2) is mentioned as a particularly preferable component.

[In the formula, R ¹ is each independently any one of aliphatic hydrocarbon group, alkoxy group, halogen atom, R ² is alkylene, k is 1 or 2, n is 0 or 1, p is 0 or 1 to An integer of 5, and q is 0 or an integer of 1 to 6. ]

By using the polyglycidyl ether of the compound (p2) together, the heat resistance of the cured product is further improved.

R ^{1 and R 2 in the aforementioned structural formula (2) have the same definitions as R 1 and R 2 in the} aforementioned structural formula (1). Regarding the hydroxyl group in the structural formula (2), k is 1 or 2, and n is 0 or 1. When k is 1, the substitution position of the hydroxyl group is preferably the 2nd position with respect to the carbon atom to which R ² is bonded. In addition, when k is 2, the substitution positions of the hydroxyl group are preferably the 2nd and 7th positions with respect to the carbon atom to which R ² is bonded. When n is 1, the substitution position of the hydroxyl group is preferably the 7th position with respect to the carbon atom to which R ² is bonded. Therefore, as a more preferable compound among the said compound (p2), the compound represented by any one of following structural formula (2-1) to (2-4) is mentioned.

[In the formula, R ¹ is each independently any one of aliphatic hydrocarbon group, alkoxy group and halogen atom, R ² is alkylene group, p is 0 or an integer of 1 to 5, and q is 0 or 1 to 6 Integer, r is 0 or an integer from 1 to 4, and s is 0 or an integer from 1 to 5. ]

In addition to the polyglycidyl ether of the compound (p2), the raw material epoxy resin (a1) may contain, for example, a bisphenol-type epoxy resin; a biphenyl-type epoxy resin; Various novolak epoxy resins with benzene, naphthol, dihydroxynaphthalene, biphenol, bisphenol, etc. as raw materials; trisphenol methane epoxy resins; dicyclopentadiene-phenol addition reaction epoxy resins; Polyarylidene ether type epoxy resins; polyglycidyl ethers of phenolic resins having a resin structure such as phenol or cresol, naphthol, biphenol, bisphenol, etc. linked by aryldialkylene groups.

The aforementioned raw material epoxy resin (a1) can be produced by any method. For example, the polyglycidyl of the aforementioned compound (p1) can be prepared separately Polyglycidyl ethers or polyglycidyl ethers of the aforementioned compound (p2), other epoxy resins can be blended, or the precursor phenol resin of each component can be blended and then polyglycidyl etherified together. method to manufacture. As a preferable method for producing the aforementioned raw material epoxy resin (a1), for example, in the presence of an alkali catalyst, various hydroxynaphthalene compounds, formaldehyde or alkyl aldehyde are heated at a temperature of about 20 to 150° C. Reaction under conditions to obtain phenol intermediate, and then its polyglycidyl etherification method. The reaction ratio of the hydroxynaphthalene compound and the aldehyde compound is preferably the ratio of the aldehyde compound in the range of 0.6 to 2.0 mol relative to 1 mol of the hydroxynaphthalene compound, and the ratio of the aldehyde compound in the range of 0.6 to 1.5 mol. for better. After completion of the reaction, it is preferable to appropriately neutralize or wash with water. Moreover, purification processes, such as reprecipitation and fine filtration, can also be performed as needed.

Examples of the alkali catalyst system include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metals such as metal sodium and metal lithium; alkali metal carbonates such as sodium carbonate and potassium carbonate. These systems may be used alone or in combination of two or more. The catalyst addition amount is preferably in the range of 0.2 to 2.0 mol relative to 1 mol of the hydroxynaphthalene compound.

The reaction can also optionally be carried out in an organic solvent. The selection of the organic solvent is appropriately selected according to the solubility of the reaction raw materials or products, the reaction temperature conditions, etc., but for example, methyl selenium, isopropanol, ethyl selenium, toluene, xylene, methyl alcohol, etc. can be mentioned. isobutyl ketone, etc. These systems can be used individually, and can also be used as a mixed solvent of 2 or more types.

The polyglycidyl etherification reaction system of the above-mentioned phenol intermediate can be carried out by a well-known and conventional method. As an example, one can cite For example, using an epihalohydrin of 2 to 10 moles relative to 1 mole of phenolic hydroxyl groups contained in the phenol intermediate, and adding 0.9 to 2.0 moles of epihalohydrin relative to 1 mole of phenolic hydroxyl groups in one or several steps A method of reacting at a temperature of 20~120°C for 0.5~10 hours while using an alkaline catalyst.

Since the aforementioned raw material epoxy resin (a1) can fully exert the effect of the present invention, the content of the polyglycidyl ether of the aforementioned compound (p1) is preferably 20% or more, more preferably 20 to 65%, particularly preferably range from 25 to 50%. When the raw material epoxy resin (a1) contains the polyglycidyl ether of the compound (p2), it becomes an acid group-containing (meth)acrylate resin excellent in the balance between ductility and heat resistance in the cured product. It can be seen that the content of the polyglycidyl ether of the aforementioned compound (p2) is preferably in the range of 1 to 30%, more preferably in the range of 2 to 20%.

The content of each component in the raw material epoxy resin (a1) is a value calculated from the area ratio of the GPC chart measured under the following conditions.

Measuring device: "HLC-8320 GPC" manufactured by TOSOH Co., Ltd., Column: Guard column "HXL-L" manufactured by TOSOH Co., Ltd.

+TOSOH Co., Ltd. "TSK-GEL G2000HXL"

+TOSOH Co., Ltd. "TSK-GEL G2000HXL"

+TOSOH Co., Ltd. "TSK-GEL G3000HXL"

+TOSOH Co., Ltd. "TSK-GEL G4000HXL"

Detector: RI (Differential Refractometer)

Data processing: "GPC WORKSTATION EcoSEC-WorkStation" manufactured by TOSOH Co., Ltd.

Measurement conditions: column temperature 40°C

Developing solvent Tetrahydrofuran

Flow rate 1.0ml/min

Standard: According to the measurement manual of the aforementioned "GPC WORKSTATION EcoSEC-WorkStation", the following monodisperse polystyrene having a known molecular weight was used.

(using polystyrene)

"A-500" manufactured by TOSOH Co., Ltd.

"A-1000" manufactured by TOSOH Co., Ltd.

"A-2500" manufactured by TOSOH Co., Ltd.

"A-5000" manufactured by TOSOH Co., Ltd.

"F-1" manufactured by TOSOH Co., Ltd.

"F-2" manufactured by TOSOH Co., Ltd.

"F-4" manufactured by TOSOH Co., Ltd.

"F-10" manufactured by TOSOH Co., Ltd.

"F-20" manufactured by TOSOH Co., Ltd.

"F-40" manufactured by TOSOH Co., Ltd.

"F-80" manufactured by TOSOH Co., Ltd.

"F-128" manufactured by TOSOH Co., Ltd.

Sample: A tetrahydrofuran solution (50 μl) that was filtered using a microfilter to convert the resin solid content to 1.0% by mass

The specific structure of the polyhydroxy compound (a2) is not particularly limited as long as it is a compound capable of reacting with the raw material epoxy resin (a1), and various polyhydroxy compounds can be used. Among them, an aromatic polyhydroxy compound is preferred because of its excellent reactivity with the raw material epoxy resin (a1). As the aromatic polyhydroxy compound, for example, dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, polyhydroxy Hydroxybiphenyl, poly(hydroxyphenyl)alkane, other bisphenol compounds, and the like, and compounds having one to plural substituents on carbon atoms of these compounds, and the like. The substituent on the carbon atom includes an aliphatic hydrocarbon group, an alkoxy group, and a halogen atom, and specific examples of each are as described above. Among them, aromatic dihydroxy compounds are preferred, and dihydroxynaphthalene or A compound having one or more substituents on its aromatic nucleus.

The reaction system of the said raw material epoxy resin (a1) and the said polyhydroxy compound (a2) can be performed in the temperature range of about 100-200 degreeC in presence of a reaction catalyst, for example. From the viewpoint of being an acid group-containing (meth)acrylate resin excellent in developability in addition to ductility and heat resistance in the cured product, the raw material epoxy resin (a1) and the above-mentioned polyhydroxy compound (a2) ) with respect to the total mass of the raw material epoxy resin (a1), the polyhydroxy compound (a2) is preferably used in the range of 0.1 to 20 mass %, and the range of 0.5 to 10 mass % It is more preferable to use the aforementioned polyhydroxy compound (a2).

Examples of the reaction catalyst system include phosphorus compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; and amine compounds such as triethylamine, tributylamine, and dimethylbenzylamine. These systems may be used independently, respectively, and may use 2 or more types together. The addition amount of the catalyst is preferably used within a range of 0.05 to 5 mass % with respect to the total mass of the raw material epoxy resin (a1) and the polyhydroxy compound (a2).

The reaction system of the said raw material epoxy resin (a1) and the said polyhydroxy compound (a2) can also be performed in an organic solvent as needed. The selection of the organic solvent to be used is appropriately selected according to the solubility of the reaction raw materials and the acid group-containing (meth)acrylate resin as the product, or the reaction temperature conditions, but for example, methyl ethyl ketone, acetone, Dimethylformamide, Methylisobutylketone, Methoxypropanol, Cyclohexanone, Methyl Salusol, Dialkylene Glycol Monoalkyl Ether Acetate, Dialkylene Glycol acetate, etc. These systems can be used individually, and can also be used as a mixed solvent of 2 or more types. From the viewpoint of achieving favorable reaction efficiency, the amount of the organic solvent used is preferably within a range of about 0.1 to 5 times the amount of the total mass of the reaction raw materials.

Examples of the unsaturated monocarboxylic acid or its derivative (B) include 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 acid anhydride thereof. These systems may be used individually or in combination of two or more.

As the polycarboxylic acid anhydride (C), any acid anhydride can be used as long as it is an acid anhydride of a compound having two or more carboxyl groups in one molecule. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, trans Anhydrides of dicarboxylic acid compounds such as butenedioic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid. The polycarboxylic acid anhydride (C) may be used alone or in combination of two or more. Among them, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, The acid anhydride of a compound having a cyclic structure in its molecular structure, such as hexahydrophthalic acid and methylhexahydrophthalic acid. Moreover, succinic anhydride is preferable from the point of becoming an acid group containing (meth)acrylate resin which is excellent in developability.

The acid group-containing (meth)acrylate resin of the present invention only requires the reaction of the epoxy resin (A), the unsaturated monocarboxylic acid or its derivative (B), and the polycarboxylic acid anhydride (C). If the raw material is used, its production method is not particularly limited, and for example, it may be any of a method of reacting all the reaction raw materials at one time, or a method of sequentially reacting all the reaction raw materials. Among them, from the viewpoint of easy control of the reaction, the following method is preferred: first, the epoxy resin (A) is reacted with an unsaturated monocarboxylic acid or a derivative (B) thereof, and then the polycarboxylic acid anhydride (C) is reacted. reaction. In the reaction system, for example, after the epoxy resin (A) and the unsaturated monocarboxylic acid or its derivative (B) are reacted in the temperature range of about 100 to 150° C. in the presence of a reaction catalyst, the reaction system can It is carried out by adding polycarboxylic anhydride (C) and reacting in a temperature range of about 90 to 120°C. Moreover, manufacture of the said epoxy resin (A) and manufacture of the (meth)acrylate resin containing an acid group can also be performed continuously.

The reaction ratio of the aforementioned epoxy resin (A) and the unsaturated monocarboxylic acid or its derivative (B) is in the range of 0.9 to 1.1 mol with respect to 1 mol of epoxy groups in the epoxy resin (A) It is preferable to use an unsaturated monocarboxylic acid or its derivative (B). In addition, the reaction ratio of the polycarboxylic acid anhydride (C) is preferably used in the range of 0.2 to 1.0 mol with respect to 1 mol of epoxy groups in the epoxy resin (A).

As the said reaction catalyst system, the compound used in the reaction of the said raw material epoxy resin (a1) and the said polyhydroxy compound (a2) can be mentioned. The addition amount of the catalyst is preferably used in the range of 0.03 to 5 mass % with respect to the total mass of the reaction raw materials. When the production of the epoxy resin (A) and the production of the acid group-containing (meth)acrylate resin are continuously performed, a new catalyst may not be added, or may be appropriately added.

The reaction can also optionally be carried out in an organic vehicle. The organic solvent system used is the same as that used in the reaction of the above-mentioned raw material epoxy resin (a1) and the above-mentioned polyhydroxy compound (a2). From the viewpoint of improving the reaction efficiency, 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.

From the viewpoint of being an acid group-containing (meth)acrylate resin excellent in developability in addition to ductility and heat resistance of the cured product, the acid of the acid group-containing (meth)acrylate resin of the present invention The value is preferably in the range of 40 to 90 mgKOH/g. In addition, in this invention, the acid value of the (meth)acrylate resin containing an acid group is the value measured using the neutralization titration method of JIS K 0070 (1992).

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

啉基苯基)-丁酮-1、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-

啉基)苯基]-1-丁酮等之烷基苯酮系光聚合起始劑；2,4,6-三甲基苯甲醯基-二苯基-氧化膦等醯基氧化膦系光聚合起始劑；二苯基酮化合物等分子內抓氫型光聚合起始劑等。此等係可個別單獨使用，亦可併用2種以上。 The aforementioned photopolymerization initiator may be appropriately selected and used according to the type of active energy ray to be irradiated. Moreover, photosensitizers, such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, a nitrile compound, may be used together. Specific examples of the photopolymerization initiator include, for example, 1-hydroxy-cyclohexyl-phenyl-one, 2-benzyl-2-dimethylamino-1-(4-N-

Linophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

Alkyl)phenyl]-1-butanone and other alkyl phenone photopolymerization initiators; 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide and other phosphonium phosphine oxides Photopolymerization initiators; intramolecular hydrogen-absorbing photopolymerization initiators such as benzophenone compounds, etc. These systems may be used individually or in combination of two or more.

Examples of commercially available types of the above-mentioned photopolymerization initiators include "IRGACURE127", "IRGACURE184", "IRGACURE250", "IRGACURE270", "IRGACURE290", "IRGACURE369E", "IRGACURE379EG", "IRGACURE500", "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 addition amount of the said photoinitiator is preferably in the range of 0.05-15 mass % with respect to the sum total of components other than the solvent of a curable resin composition, for example, More preferably, it is the range of 0.1-10 mass %.

The curable resin composition of the present invention may contain resin components other than the above-mentioned acid group-containing (meth)acrylate resin of the present invention. Examples of the resin component include reacting epoxy resins such as bisphenol-type epoxy resins and novolak-type epoxy resins with (meth)acrylic acid, dicarboxylic acid anhydrides, and optionally added unsaturated monocarboxylic acid anhydrides, and the like. The obtained resin has a carboxyl group and a (meth)acryloyl group in the resin, various (meth)acrylate monomers, and the like.

Examples of the (meth)acrylate monomer system include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylate. Aliphatic mono(meth)acrylate compounds such as amyl acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate; (meth)acrylic acid ring Alicyclic mono(meth)acrylate compounds such as hexyl ester, isobornyl (meth)acrylate, adamantyl mono(meth)acrylate; Cyclic mono(meth)acrylate compound; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, (meth)acrylate base) phenoxyethyl acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzene (meth)acrylate Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as methyl ester, benzyl benzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc.; (poly)oxyalkylene modified by introducing polyoxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxybutylene chains into the molecular structure of the aforementioned various mono(meth)acrylate monomers Mono(meth)acrylate compound; Lactone-modified mono(meth)acrylate compound with (poly)lactone structure introduced into the molecular structure of the aforementioned various mono(meth)acrylate compounds; Ethylene glycol diacrylate (Meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc. Aliphatic di(meth)acrylate compound; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornanedimethanol di(meth)acrylic acid Esters, dicyclopentenyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate and other alicyclic di(meth)acrylate compounds; biphenol di(meth)acrylate , Aromatic di(meth)acrylate compounds such as bisphenol di(meth)acrylate; Introduce (poly)ethylene oxide chain, (poly)propylene oxide into the molecular structure of the aforementioned various di(meth)acrylate compounds Polyoxyalkylene-modified di(meth)acrylate compounds of (poly)oxyalkylene chains such as chains, (poly)oxybutylene chains, etc.; Lactone-modified di(meth)acrylate compounds with lactone structure; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerol tri(meth)acrylate ; Introduce (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, (poly) oxybutylene chains, etc. into the molecular structure of the aforementioned aliphatic tri(meth)acrylate compound (poly) Oxyalkylene-modified tri(meth)acrylate compound; in the aforementioned aliphatic tri(meth)acrylate compound Introduce (poly) lactone structure into the molecular structure of lactone modified tri (meth) acrylate compound; neotaerythritol tetra (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate , aliphatic poly(meth)acrylate compounds with more than 4 functions, such as dipivoerythritol hexa(meth)acrylate; (poly)oxidation is introduced into the molecular structure of the aforementioned aliphatic poly(meth)acrylate compounds (poly)oxyalkylene-modified poly(meth)acrylate compounds with tetrafunctional or more (poly)oxyalkylene chains such as ethylene chains, (poly)oxypropylene chains, (poly)oxybutylene chains, etc.; in the aforementioned aliphatic polymers A lactone-modified poly(meth)acrylate compound having a (poly)lactone structure of tetrafunctional or higher is introduced into the molecular structure of the (meth)acrylate compound.

等環狀醚溶劑；乙酸甲酯、乙酸乙酯、乙酸丁酯等酯；甲苯、二甲苯等芳香族溶劑；環己烷、甲基環己烷等脂環族溶劑；卡必醇、賽路蘇、甲醇、異丙醇、丁醇、丙二醇單甲基醚等醇溶劑；伸烷基二醇單烷基醚、二伸烷基二醇單烷基醚、二伸烷基二醇單烷基醚乙酸酯等二醇醚系溶劑。此等係可個別單獨使用，亦可併用2種以上。 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 kind and addition amount are appropriately adjusted depending on the desired performance. Generally, it is used in the range of 10-90 mass % with respect to the total of curable resin composition. Specific examples of the aforementioned solvent include, for example, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone;

and other cyclic ether solvents; esters such as methyl acetate, ethyl acetate, butyl acetate, etc.; aromatic solvents such as toluene and xylene; alicyclic solvents such as cyclohexane and methylcyclohexane; Alcohol solvents such as threo, methanol, isopropanol, butanol, propylene glycol monomethyl ether; Glycol ether solvents such as ether acetate. These systems may be used individually or in combination of two or more.

In addition, the curable resin composition of the present invention may contain various additives such as inorganic fine particles or 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 of ductility and heat resistance in the cured product. In general, in order to improve the ductility of the cured product, it is necessary to introduce a soft structure into the resin structure, but in this case, the heat resistance of the cured product tends to decrease significantly. The acid group-containing (meth)acrylate resin of the present invention has a performance that subverts the conventional technical common sense in that it has these difficult-to-have performances at a high level at the same time. The acid group-containing (meth)acrylate resin of the present invention can be used in applications in which the balance between the ductility and heat resistance of the cured product is excellent, for example, in applications related to semiconductor devices. Solder resists, interlayer insulating materials, encapsulation materials, underfill materials, adhesive layers for encapsulation of circuit elements, etc., or adhesive layers for integrated circuit elements and circuit boards are used. In addition, in terms of applications related to thin displays represented by LCD and OELD, it can be applied to thin film transistor protective films, liquid crystal color filter protective films, pigment photoresists for color filters, photoresists for black matrices, spacers, etc.

Moreover, since the (meth)acrylate resin containing an acid group of this invention is excellent in developability in addition to ductility and heat resistance in hardened|cured material, it can be suitably used for a soldering resist application. The resin material for a solder resist of the present invention contains, for example, various components such as a curing agent, a curing accelerator, and an organic solvent, in addition to the aforementioned acid group-containing (meth)acrylate resin, a photopolymerization initiator, and various additives.

The said hardening|curing agent will not be specifically limited if it has a functional group which can react with the carboxyl group in the said acid group containing (meth)acrylate resin, For example, an epoxy resin is mentioned. The epoxy resins used here include, for example, bisphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthyl-extended ether-type epoxy resins, biphenyl-type epoxy resins, and triphenylmethane-type epoxy resins. Oxygen resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol novolak epoxy resin, naphthol novolak epoxy resin, naphthol-phenol co-asol novolak epoxy resin , Naphthol-cresol co-acetal type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, etc. These systems may be used individually or in combination of two or more. Among these epoxy resins, phenol novolac epoxy resins, cresol novolak epoxy resins, bisphenol novolak epoxy resins, bisphenol novolak epoxy resins, Novolak epoxy resins such as naphthol novolak epoxy resin, naphthol-phenol co- novolak epoxy resin, naphthol-cresol co-deal novolak epoxy resin, etc., particularly preferably a softening point of 50 ~120°C range.

The hardening accelerator promotes the hardening reaction of the hardener, and when epoxy resin is used as the hardener, phosphorus-based compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, ammonium zirconium salts, etc. are mentioned. These systems may be used individually or in combination of two or more. The addition amount of a hardening accelerator is used in the range of 1-10 mass parts with respect to 100 mass parts of said hardening|curing agents, for example.

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

The method of obtaining a photoresist member using the resin material for solder resists of the present invention includes, for example, the following method: apply the resin material for solder resists to a base material, and volatilize an organic solvent at a temperature of about 60 to 100° C. After drying, it is exposed to ultraviolet rays or electron beams through a photomask with a desired pattern, and the unexposed part is developed with an aqueous alkaline solution, and then heated and hardened at a temperature range of about 140 to 180°C.

[Example]

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples.

The content of each component in the epoxy resin (a1) was calculated from the area ratio of the GPC chart measured under the following conditions.

Measuring device: "HLC-8320 GPC" manufactured by TOSOH Co., Ltd., Column: Guard column "HXL-L" manufactured by TOSOH Co., Ltd. + "TSK-GEL G2000HXL" manufactured by TOSOH Co., Ltd. + "TSK-GEL G2000HXL" manufactured by TOSOH Co., Ltd. TSK-GEL G2000HXL" + TOSOH Co., Ltd. "TSK-GEL G3000HXL" + TOSOH Co., Ltd. "TSK-GEL G4000HXL"

Detector: RI (Differential Refractometer)

Data processing: "GPC WORKSTATION EcoSEC-WorkStation" manufactured by TOSOH Co., Ltd.

Measurement conditions: column temperature 40°C

Developing solvent Tetrahydrofuran

Flow rate 1.0ml/min

Standard: The following monodisperse polystyrene whose molecular weight is known is used according to the measurement manual of the aforementioned "GPC WORKSTATION EcoSEC-WorkStation".

(using polystyrene)

"A-500" manufactured by TOSOH Co., Ltd.

"A-1000" manufactured by TOSOH Co., Ltd.

"A-2500" manufactured by TOSOH Co., Ltd.

"A-5000" manufactured by TOSOH Co., Ltd.

"F-1" manufactured by TOSOH Co., Ltd.

"F-2" manufactured by TOSOH Co., Ltd.

"F-4" manufactured by TOSOH Co., Ltd.

"F-10" manufactured by TOSOH Co., Ltd.

"F-20" manufactured by TOSOH Co., Ltd.

"F-40" manufactured by TOSOH Co., Ltd.

"F-80" manufactured by TOSOH Co., Ltd.

"F-128" manufactured by TOSOH Co., Ltd.

Sample: A tetrahydrofuran solution (50 μl) that was filtrated with a resin solid content of 1.0% by mass using a microfilter

The MS data and C ¹³ NMR of the epoxy resin (a1) were measured by the following apparatus.

MS: Double Focusing Mass Spectrometer AX505H (FD505H) manufactured by Nippon Electronics Co., Ltd.

NMR: Nippon Electronics Co., Ltd. NMR GSX270

In the examples of this case, the acid value of the (meth)acrylate resin containing acid groups was measured by the neutralization titration method of JIS K 0070 (1992).

Production Example 1 Production of epoxy resin (a1)

240 g of 2,7-dihydroxynaphthalene, 85 g of a 37% by mass formaldehyde solution, 376 g of isopropanol, and 88 g of a 48% aqueous potassium hydroxide solution were charged into a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer. . Stirring was started while blowing in nitrogen, heated to 75°C and stirred for 2 hours. After completion of the reaction, 108 g of sodium dihydrogen phosphate was added for neutralization. Isopropanol was removed under reduced pressure and 480 g of methyl isobutyl ketone was added. After adding 200 g of water and repeating the water washing operation three times, methyl isobutyl ketone was removed under heating and decompression conditions to obtain 245 g of a phenol resin intermediate having a hydroxyl group equivalent of 84 g/equivalent.

Nitrogen flushing was performed in a flask equipped with a thermometer, a cooling pipe, and a stirrer, and at the same time, 84 g of the previously obtained phenol resin intermediate, 463 g of epichlorohydrin, and 53 g of n-butanol were fed and dissolved. After heating to 50 degreeC, 220 g of 20% sodium hydroxide aqueous solution was added over 3 hours, and it was made to react for another 1 hour. After completion of the reaction, the unreacted epichlorohydrin was distilled off under reduced pressure by heating to 150°C. To the obtained crude product, 300 g of methyl isobutyl ketone and 50 g of n-butanol were added and dissolved. Next, 15 g of a 10 mass % sodium hydroxide aqueous solution was further added, and the reaction was carried out at 80° C. for 2 hours. After washing with water until the pH of the washing liquid becomes neutral, the system is azeotropically dehydrated. After microfiltration, the solvent was distilled off under reduced pressure to obtain 126 g of epoxy resin (a1). The softening point of the epoxy resin (a1) was 95°C (B&R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150°C) was 9.0 dPa·s, and the epoxy equivalent was 174 g/equivalent. In the C ¹³ NMR chart, it was confirmed that there was a peak indicating the presence of a carbonyl group in the vicinity of 203 ppm. Further, in the MS spectrum, a peak of 512 showing the existence of the compound represented by the following structural formula (x1) and a peak of 556 showing the existence of the compound represented by the following structural formula (x2) were confirmed. The epoxy resin (a1) contains 10% of the compound represented by the following structural formula (x1), 40% of the compound represented by the following structural formula (x2), and 50% of other oligomers.

Example 1 Production of acid group-containing (meth)acrylate resin (1)

Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 105 g of diethylene glycol monomethyl ether acetate, 190 g of the epoxy resin (a1) obtained previously, and 5 g of 2,7-dihydroxynaphthalene were charged, and the dissolve. 0.7 g of dibutylhydroxytoluene and 1.3 g of triphenylphosphine were added, and the mixture was reacted at 150° C. for 2 hours under a nitrogen atmosphere. 0.1 g of hydroquinone monomethyl ether and 74 g of acrylic acid were added, and the mixture was reacted at 120° C. for 10 hours while blowing in air. 105 g of diethylene glycol monomethyl ether acetate and 73 g of tetrahydrophthalic anhydride were added, and the mixture was reacted at 110° C. for 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 80 mgKOH/g. The GPC chart of the acid group-containing (meth)acrylate resin (1) is shown in FIG. 1 .

Example 2 Production of acid group-containing (meth)acrylate resin (2)

Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 105 g of diethylene glycol monomethyl ether acetate, 190 g of the epoxy resin (a1) obtained previously, and 5 g of 2,7-dihydroxynaphthalene were charged, and the dissolve. 0.7 g of dibutylhydroxytoluene and 1.3 g of triphenylphosphine were added, and the mixture was reacted at 150°C for 2 hours under a nitrogen atmosphere. 0.1 g of hydroquinone monomethyl ether and 74 g of acrylic acid were added, and the mixture was reacted at 120° C. for 10 hours while blowing in air. 87 g of diethylene glycol monomethyl ether acetate and 44 g of succinic anhydride were added, and the mixture was reacted at 110° C. for 5 hours to obtain an 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.

Comparative Production Example 1 Production of Acid Group-Containing (Meth)acrylate Resin (1')

Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 87 g of diethylene glycol monomethyl ether acetate, 1,1-bis(2,7-glycidoxynaphthyl)methane ( 162 g of "EPICLON HP-4700, epoxy equivalent 162 g/equivalent) manufactured by DIC Co., Ltd. was dissolved. 0.6 g of dibutylhydroxytoluene, 0.1 g of hydroquinone monomethyl ether as a thermal polymerization inhibitor, 72 g of acrylic acid, and triphenylene were added. 1.2 g of phosphine was reacted at 120° C. for 10 hours while blowing in air. 95 g of diethylene glycol monomethyl ether acetate and 64 g of tetrahydrophthalic anhydride were added, and the reaction was conducted at 110° C. for 5 hours to obtain an acid containing The (meth)acrylate resin (1') of the base. The acid value of the solid content of the acid group-containing (meth)acrylate resin (1') was 80 mgKOH/g.

Examples 3, 4 and Comparative Example 1

A curable resin composition was prepared according to the following points, and various evaluation tests were performed. Table 1 shows the results.

◆Evaluation of heat resistance and ductility of hardened products ‧Preparation of curable resin composition

啉丙烷-1-酮]5g、BASF公司製「IRGACURE TPO」(2,4,6-三甲基苯甲醯基-二苯基-氧化膦)3g、二乙二醇單甲基醚乙酸酯13g，得到硬化性樹脂組成物。 100 g of the acid group-containing (meth)acrylate resin previously obtained, 24 g of "EPICLON N-680" (cresol novolak type epoxy resin) manufactured by DIC Co., Ltd., and "IRGACURE 907" manufactured by BASF Corporation [2 -Methyl-1-(4-methylthiophenyl)-2-N-

Linopropan-1-one] 5 g, BASF Corporation "IRGACURE TPO" (2,4,6-trimethylbenzyl-diphenyl-phosphine oxide) 3 g, diethylene glycol monomethyl ether acetic acid 13 g of esters were used to obtain a curable resin composition.

‧Preparation of hardened material

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

‧Evaluation of heat resistance of cured products

A test piece of 6 mm × 40 mm was cut out from the cured product, and the elastic modulus was measured using a viscoelasticity measuring apparatus (DMA: Solid viscoelasticity measuring apparatus "RSAII" manufactured by Rheometric Corporation, tensile method: frequency 1 Hz, heating rate 3°C/min). The temperature at which the number change became the largest (tan δ change rate was the largest) was evaluated as the glass transition temperature (Tg).

‧Evaluation of ductility of hardened product

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

Temperature 23℃, humidity 50%, distance between marking lines 20mm, distance between fulcrums 20mm, stretching speed 10mm/min

◆Evaluation of quick-drying, light sensitivity and drying management range ‧Preparation of curable resin composition

啉丙烷-1-酮]5g、BASF公司製「IRGACURE TPO」(2,4,6-三甲基苯甲醯基-二苯基-氧化膦)3g、二乙二醇單甲基醚乙酸酯13g、作為顏料的酞花青綠0.65g，以輥磨機進行揑揉得到硬化性樹脂組成物。 100 g of the acid group-containing (meth)acrylate resin previously obtained, 24 g of "EPICLON N-680" (cresol novolak type epoxy resin) manufactured by DIC Co., Ltd., and "Rumikhua DPA" manufactured by Toagosei Co., Ltd. -600T" (a composition containing dipeptaerythritol pentaacrylate and dipeptaerythritol hexaacrylate in a molar ratio of 40/60) 10 g, "IRGACURE 907" manufactured by BASF Corporation [2-methyl-1- (4-Methylthiophenyl)-2-N-

Linopropan-1-one] 5 g, BASF Corporation "IRGACURE TPO" (2,4,6-trimethylbenzyl-diphenyl-phosphine oxide) 3 g, diethylene glycol monomethyl ether acetic acid 13 g of ester and 0.65 g of phthalocyanine green as a pigment were kneaded with a roll mill to obtain a curable resin composition.

‧Evaluation of quick drying

The curable resin composition was applied on a glass substrate with a coater of 50 μm, and dried at 80° C. for 30 minutes. Put a polyethylene terephthalate (PET) film on the surface of the coating film, and then place a weight of 50g for 10 seconds. The polyethylene terephthalate (PET) film that did not adhere when lifted was rated as A, An adhesion-producing person was designated as B for evaluation.

‧Measurement of light sensitivity

The curable resin composition was applied on a glass substrate with a coater of 50 μm, and dried at 80° C. for 30 minutes. Next, ultraviolet rays of 1000 mJ/cm ² were irradiated with a metal halide lamp through a step tablet No. 2 manufactured by Kodak Corporation. This was developed with a 1 mass % sodium carbonate aqueous solution for 180 seconds, and evaluated by the number of remaining stages. The more the remaining series, the higher the light sensitivity.

‧Determination of drying management range

The curable resin composition was applied on a glass substrate with a 50 μm applicator, and samples having drying times at 80° C. of 30 minutes, 40 minutes, 50 minutes, and 60 minutes were prepared. These samples were developed with a 1 mass % sodium carbonate aqueous solution for 180 seconds, and the drying time at 80° C. of the samples without residues was evaluated as a drying control range. The longer the drying control range is, the better the alkali developability is shown.

Claims (8)

A (meth)acrylate resin containing an acid group, which uses epoxy resin (A), unsaturated monocarboxylic acid or its derivative (B) and polycarboxylic acid anhydride (C) as necessary reaction raw materials, characterized by In that the epoxy resin (A) is the reaction product of the raw epoxy resin (a1) and the polyhydroxy compound (a2), wherein the raw epoxy resin (a1) is a bis(hydroxynaphthyl)alkane compound (p1) In addition to the polyglycidyl ether of the bis(hydroxynaphthyl)alkane compound (p1), the raw epoxy resin (a1) contains the following structural formula (2) Polyglycidyl ether of compound (p2) represented by

[In the formula, R ¹ is each independently any one of aliphatic hydrocarbon group, alkoxy group, halogen atom, R ² is alkylene, k is 1 or 2, n is 0 or 1, p is 0 or 1 to an integer of 5, and q is 0 or an integer of 1 to 6]. The acid group-containing (meth)acrylate resin of claim 1, wherein the bis(hydroxynaphthyl)alkane compound (p1) is a compound represented by the following structural formula (1)

[In the formula, R ¹ is each independently any one of aliphatic hydrocarbon group, alkoxy group and halogen atom, R ² is an alkylene group, k is 1 or 2, and l is 0 or an integer of 1 to 6]. The acid group-containing (meth)acrylate resin of claim 1, wherein the polyhydroxy compound (a2) is an aromatic dihydroxy compound. A curable resin composition comprising the acid group-containing (meth)acrylate resin according to claim 1 and a photopolymerization initiator. A hardened product, which is a hardened product of the curable resin composition of claim 4. An insulating material comprising the curable resin composition of claim 4. A resin material for a solder resist comprising the curable resin composition of claim 4. A photoresist member using the resin material for solder resist as claimed in claim 7.

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