KR20190137075A - Acid group-containing (meth) acrylate resins and resin materials for solder resists - Google Patents

Abstract

This invention is an acidic radical containing (meth) acrylate resin which makes epoxy resin (A), unsaturated monocarboxylic acid or its derivative (B), and polycarboxylic acid anhydride (C) an essential reaction raw material, The said epoxy resin (A) (A) An acid group characterized by being a reaction product of a raw material epoxy resin (a1) containing polyglycidyl ether of a bis (hydroxynaphthyl) alkane compound (p1) as an essential component and a polyhydroxy compound (a2). A containing (meth) acrylate resin is provided. This acid group containing (meth) acrylate resin can form the hardened | cured material excellent in elongation and heat resistance.

Description

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

The present invention provides an acid group-containing (meth) acrylate resin having excellent balance between elongation and heat resistance in the cured product, a curable resin composition containing the same, an insulating material composed of the curable resin composition, a resin material for solder resist, and a resist member. It is about.

BACKGROUND ART Acid group-containing epoxy acrylate resins obtained by reacting an acid anhydride after acrylateizing an epoxy resin with acrylic acid are widely used in the resin material for soldering resists for printed wiring boards. The required performance of the resin material for soldering resist is various, such as hardening with a small exposure amount, being excellent in alkali developability, being excellent in heat resistance, strength, flexibility, elongation, dielectric property, etc. in hardened | cured material. .

As a conventionally known solder resist resin material, an acid group-containing epoxy acrylate resin obtained by reacting 1,1-bis (2,7-glycidyloxynaphthyl) methane with acrylic acid and tetrahydrophthalic anhydride is known (following). See Patent Document 1). Although the acidic radical containing epoxy acrylate resin of patent document 1 has the characteristic which is excellent in heat resistance compared with the acidic radical containing epoxy acrylate resin which uses a phenol novolak-type epoxy resin as a raw material, elongation in hardened | cured material is very low, and Since cracks tend to occur easily and reliability is inferior, there existed subjects, such as being unsuitable for the use which requires flexibility, such as a flexible board | substrate.

Japanese Patent Laid-Open No. 2001-89644

Therefore, the subject which this invention tries to solve is an acidic radical containing (meth) acrylate resin excellent in the balance of elongation and heat resistance in hardened | cured material, the curable resin composition containing this, the insulating material which consists of said curable resin composition, and a solder It is providing a resist resin material and a resist member.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, as an epoxy resin which is a reaction raw material of an acidic radical containing epoxy (meth) acrylate resin, the polyglycidyl ether of a bis (hydroxynaphthyl) alkane compound is essential. By using the reaction product of the raw material epoxy resin as a component and a polyhydroxy compound, it becomes a resin material excellent in the balance of elongation and heat resistance in hardened | cured material, maintaining performance, such as photosensitivity and alkali developability. It was found out and completed the present invention.

That is, this invention is an acidic radical containing (meth) acrylate resin which makes an epoxy resin (A), unsaturated monocarboxylic acid or its derivative (B), and polycarboxylic acid anhydride (C) an essential reaction raw material, The said epoxy resin ( A) contains the acidic radical which is a reaction product of the raw material epoxy resin (a1) which makes the polyglycidyl ether of the bis (hydroxynaphthyl) alkane compound (p1) an essential component, and a polyhydroxy compound (a2) ( It relates to a meta) acrylate resin.

This invention also relates to the curable resin composition containing the said acidic radical containing (meth) acrylate resin and a photoinitiator.

This invention relates to the hardened | cured material of the said curable resin composition further.

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

This invention relates also to the resin material for soldering resists which consists of the said curable resin composition.

The present invention also 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 having excellent balance between elongation and heat resistance in a cured product, a curable resin composition containing the same, an insulating material composed of the curable resin composition, a resin material for a solder resist, and a resist The member can be provided.

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

Hereinafter, the present invention will be described in detail.

The acidic radical containing (meth) acrylate resin of this invention is acidic radical containing (meth) acrylate which makes epoxy resin (A), unsaturated monocarboxylic acid or its derivative (B), and polycarboxylic acid anhydride (C) an essential reaction raw material. As a resin, the said epoxy resin (A) is a raw material epoxy resin (a1) which makes a polyglycidyl ether of a bis (hydroxynaphthyl) alkane compound (p1) an essential component, a polyhydroxy compound (a2), It is characterized in that the reaction product of.

In this invention, (meth) acrylate resin means resin which has an acryloyl group, a methacryloyl group, or both in a molecule | numerator. In addition, a (meth) acryloyl group means one or both of an acryloyl group and a methacryloyl group, and (meth) acrylate is a general term of acrylate and methacrylate.

The said epoxy resin (A) is a reaction product of the raw material epoxy resin (a1) which makes polyglycidyl ether of a bis (hydroxynaphthyl) alkane compound (p1) an essential component, and a polyhydroxy compound (a2). to be. The said characteristic is an essential requirement for obtaining the acidic radical containing (meth) acrylate resin excellent in the balance of elongation and heat resistance in hardened | cured material.

As long as the bis (hydroxynaphthyl) alkane compound (p1) has a structure in which a naphthalene skeleton having one or more hydroxy groups is bonded to an alkylene group, other specific structures are not particularly limited, and various kinds can be used. . As one of the preferable specific examples, the following structural formula (1)

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

The compound represented by these is mentioned. The bis (hydroxynaphthyl) alkane compound (p1) may be used individually by 1 type, and may use two or more types together.

With respect to R ¹ in the structural formula (1), the aliphatic hydrocarbon group may be linear, branched, or may have one or more unsaturated bonds. In addition, the number of carbon atoms is especially regardless. Especially, since it becomes the acid-group-containing (meth) acrylate resin which is more excellent in the balance of elongation and heat resistance in hardened | cured material, it is preferable that it is a C1-C6 alkyl group. Examples of the alkoxy group include an alkoxy group having about 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, a propyloxy group, a butyloxy group, a pentyloxy group, and a hexyloxy group. Examples of the halogen atom include a chlorine atom, bromine atom, and iodine atom.

With respect to R ² in the structural formula (1), the number of carbon atoms in the alkylene group is particularly regardless. Especially, since it becomes the acid-group-containing (meth) acrylate resin which is more excellent in the balance of elongation and heat resistance in hardened | cured material, it is preferable that it is a C1-C6 alkylene group, and it is C1-C3 It is more preferable that it is an alkylene group.

With respect to the hydroxyl group in the said structural formula (1), k is 1 or 2, and two k may mutually be the same and may differ. When k is 1, it is preferable that the substituted position of a hydroxyl group is 2-position with respect to the carbon atom to which R <^2> couple | bonds. In addition, when k is 2, it is preferable that it is 2 positions and 7 positions with respect to the carbon atom to which R <^2> couple | bonds. Therefore, as a more preferable thing of the said compound (a1), what is represented by either of following structural formula (1-1)-(1-3) is mentioned.

[Wherein, R ¹ is each independently an aliphatic hydrocarbon group, an alkoxy group or a halogen atom, and R ² is an alkylene group. l is 0 or an integer of 1 to 6, m is 0 or an integer of 1 to 5]

The raw material epoxy resin (a1) may contain other components in addition to the polyglycidyl ether of the compound (p1). As especially preferable among other components, following structural formula (2)

[Wherein, R ¹ is each independently an aliphatic hydrocarbon group, an alkoxy group or a halogen atom, and R ² is an alkylene group. k is 1 or 2, n is 0 or 1, p is 0 or an integer of 1 to 5, q is 0 or an integer of 1 to 6]

The polyglycidyl ether of compound (p2) shown by is mentioned. By using polyglycidyl ether of compound (p2) together, the heat resistance of hardened | cured material becomes further higher.

R ¹ and R ² in the structural formula (2) are synonymous with those in the structural formula (1). For the hydroxyl group in the structural formula (2), k is 1 or 2 and n is 0 or 1. When k is 1, it is preferable that the substituted position of a hydroxyl group is 2-position with respect to the carbon atom to which R <^2> couple | bonds. In addition, when k is 2, it is preferable that it is 2 positions and 7 positions with respect to the carbon atom to which R <^2> couple | bonds. When n is 1, it is preferable that it is 7-position with respect to the carbon atom which R <^2> couple | bonds. Therefore, as a more preferable thing of the said compound (p2), what is represented by either of following structural formulas (2-1)-(2-4) is mentioned.

[Wherein, R ¹ is each independently an aliphatic hydrocarbon group, an alkoxy group or a halogen atom, and R ² is an alkylene group. p is an integer of 0 or 1-5, q is an integer of 0 or 1-6, r is an integer of 0 or 1-4, s is an integer of 0 or 1-5]

The said raw material epoxy resin (a1) is bisphenol-type epoxy resin other than the polyglycidyl ether of the said compound (p2); Biphenyl type epoxy resins; Various novolac-type epoxy resins which use phenol, cresol, dihydroxybenzene, naphthol, dihydroxynaphthalene, biphenol, bisphenol, etc. as a raw material; Triphenol methane type epoxy resins; Dicyclopentadiene-phenol addition reaction type epoxy resin; Polyarylene ether type epoxy resins; Phenol, cresol, naphthol, biphenol, bisphenol, etc. may contain polyglycidyl ether etc. of the phenol resin which has a resin structure connected with the arylene dialkylene group.

What was manufactured may be sufficient as the said raw material epoxy resin (a1). For example, you may separately prepare and mix the polyglycidyl ether of the said compound (p1), the polyglycidyl ether of the said compound (p2), and another epoxy resin, and mix | blended the precursor phenol resin of each component, You may manufacture by the method of carrying out polyglycidyl ether collectively after that. As one preferable method for producing the raw material epoxy resin (a1), for example, various hydroxy naphthalene compounds and formaldehyde or alkylaldehyde are reacted under temperature conditions of about 20 to 150 ° C in the presence of an alkali catalyst to phenol. The method of obtaining an intermediate and polyglycidyl etherification is mentioned. The reaction ratio between the hydroxy naphthalene compound and the aldehyde compound is preferably a ratio in which the aldehyde compound is in the range of 0.6 to 2.0 moles, and more preferably in the range of 0.6 to 1.5 moles with respect to 1 mole of the hydroxy naphthalene compound. desirable. After completion | finish of reaction, it is preferable to perform an appropriate neutralization and water washing process. Moreover, you may perform purification processes, such as reprecipitation and microfiltration, as needed.

Examples of the alkali catalyst 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 and the like. These may be used independently, respectively and may use two or more types together. It is preferable that catalyst addition amount is 0.2-2.0 mol with respect to 1 mol of hydroxy naphthalene compounds.

You may perform reaction in an organic solvent as needed. The organic solvent is appropriately selected depending on the solubility of the reaction raw material or the product, the reaction temperature conditions, and the like. For example, methyl cellosolve, isopropyl alcohol, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, and the like are selected. Can be mentioned. These may be used independently, respectively and may be used as two or more types of mixed solvents.

The polyglycidyl etherification reaction of the said phenol intermediate can be performed by a well-known method. As an example, 0.9-2.0 mol of basic catalyst can be used with respect to 1 mol of phenolic hydroxyl groups using 2-10 mol of epihalohydrin with respect to 1 mol of phenolic hydroxyl groups which the said phenol intermediate contains, for example. The method of making it react for 0.5 to 10 hours at the temperature of 20-120 degreeC, carrying out batch or division addition is mentioned.

Since the effect which this invention exhibits fully exhibits the said raw material epoxy resin (a1), it is preferable that content of the polyglycidyl ether of the said compound (p1) is 20% or more, and it is more preferable that it is 20 to 65% of range. And it is especially preferable that it is 25 to 50% of range. When the said raw material epoxy resin (a1) contains the polyglycidyl ether of the said compound (p2), since it becomes an acidic radical containing (meth) acrylate resin excellent in the balance of elongation and heat resistance in hardened | cured material, the said compound It is preferable that it is the ratio which becomes content of the polyglycidyl ether of (p2) in the range of 1 to 30%, and it is more preferable that it is the range of 2 to 20%.

Content of each component in a raw material epoxy resin (a1) is a value computed from the area ratio of the GPC chart figure measured on the following conditions.

Measuring apparatus: "HLC-8320 GPC" manufactured by Tosoh Corp.

Column: Guard column "HXL-L" made by Tosoh Corp.

    `` TSK-GEL G2000HXL '' made by + Toso Corporation

    `` TSK-GEL G2000HXL '' made by + Toso Corporation

    `` TSK-GEL G3000HXL '' made by + Toso Corporation

    `` TSK-GEL G4000HXL '' made by + Toso Corporation

Detector: RI (Differential Refractometer)

Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corp.

Measurement condition: column temperature 40 ℃

            Developing solvent tetrahydrofuran

            Flow rate 1.0ml / min

Standard: Based on the measurement manual of "GPC Workstation EcoSEC-WorkStation", the following monodisperse polystyrene whose molecular weight is known was used.

 (Use Polystyrene)

  "A-500" made by Toso Corporation

  "A-1000" made by Toso Corporation

  "A-2500" made by Toso Corporation

  "A-5000" made by Toso Corporation

  "F-1" made by Toso Corporation

  "F-2" made by Toso Corporation

  "F-4" made by Toso Corporation

  "F-10" made by Toso Corporation

  "F-20" made by Toso Corporation

  "F-40" made by Toso Corporation

  "F-80" made by Toso Corporation

  "F-128" made by Toso Corporation

Sample: 1.0 mass% tetrahydrofuran solution was filtered with a micro filter in terms of resin solid content (50 μl).

As long as the said polyhydroxy compound (a2) is a compound which can react with the said raw material epoxy resin (a1), the specific structure is not specifically limited, A variety of things can be used. Especially, since it is excellent in reactivity with the raw material epoxy resin (a1), an aromatic polyhydroxy compound is preferable. As an aromatic polyhydroxy compound, for example, dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, for example. And tetrahydroxyanthracene, polyhydroxybiphenyl, poly (hydroxyphenyl) alkane, other bisphenol compounds, and the like, and compounds having one or more substituents on the carbon atoms of these compounds. Substituents on a carbon atom include an aliphatic hydrocarbon group, an alkoxy group, and a halogen atom, and each specific example is as described above. Especially, since it becomes the acid-group-containing (meth) acrylate resin which is more excellent in the balance of elongation and heat resistance in hardened | cured material, it is preferable that it is an aromatic dihydroxy compound, and it is one on a dihydroxy naphthalene or its aromatic nucleus. Preferred are compounds having a plurality of substituents.

Reaction 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, for example in presence of a reaction catalyst. Since the reaction ratio between the raw material epoxy resin (a1) and the polyhydroxy compound (a2) is an acid group-containing (meth) acrylate resin having excellent developability in addition to elongation and heat resistance in the cured product, the raw material epoxy resin ( It is preferable to use the said polyhydroxy compound (a2) in 0.1-20 mass% with respect to the gross mass of a1), and it is more preferable to use it in 0.5-10 mass%.

Examples of the reaction catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine and triphenylphosphine, and amine compounds such as triethylamine, tributylamine and dimethylbenzylamine. These may be used independently, respectively and may use two or more types together. It is preferable to use the addition amount of a catalyst in 0.05-5 mass% with respect to the total mass of the said raw material epoxy resin (a1) and the said polyhydroxy compound (a2).

You may perform reaction of the said raw material epoxy resin (a1) and the said polyhydroxy compound (a2) in an organic solvent as needed. The selection of the organic solvent to be used is appropriately selected depending on the solubility of the reaction raw material and the acid group-containing (meth) acrylate resin that is the product, and the reaction temperature conditions. For example, methyl ethyl ketone, acetone, dimethylformamide, methyl iso Butyl ketone, methoxy propanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate, and the like. These may be used independently, respectively and may be used as two or more types of mixed solvents. Since the reaction efficiency becomes favorable for the usage-amount of the organic solvent, it is preferable to use in about 0.1-5 times the range with respect to the total mass of a reaction raw material.

Examples of the unsaturated monocarboxylic acid or its derivative (B) include compounds having a (meth) acryloyl group and a carboxyl group in one molecule such as acrylic acid and methacrylic acid, acid halides and acid anhydrides thereof. These may be used independently, respectively and may use two or more types together.

As long as the said polycarboxylic acid anhydride (C) is an acid anhydride of the compound which has two or more carboxyl groups in one molecule, any 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, hexahydrophthalic acid And acid anhydrides of dicarboxylic acid compounds such as methyl hexahydrophthalic acid. Polycarboxylic acid anhydride (C) may be used independently, respectively and may use two or more types together. Especially, in the point which becomes acid-containing (meth) acrylate resin excellent in the heat resistance in hardened | cured material, cyclic structure in molecular structures, such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, etc. Acid anhydrides of compounds having Moreover, a succinic anhydride is preferable at the point which becomes acid-containing (meth) acrylate resin excellent in developability.

The acid-group containing (meth) acrylate resin of this invention is a manufacturing method, if the said epoxy resin (A), the said unsaturated monocarboxylic acid or its derivative (B), and the said polycarboxylic anhydride (C) are essential reaction raw materials. Is not specifically limited, For example, the method of making all the reaction raw materials react collectively, the method of making it react sequentially, or any may be sufficient as it. Especially, since control of reaction is easy, the method of first making the said epoxy resin (A), unsaturated monocarboxylic acid, or its derivative (B) react, and then making the said polycarboxylic acid anhydride (C) react. The reaction is, for example, after reacting the epoxy resin (A) and unsaturated monocarboxylic acid or its derivative (B) in the temperature range of about 100 to 150 ℃ in the presence of a reaction catalyst, the polycarboxylic acid anhydride ( C) can be added and it can carry out by the method etc. which make it react in the temperature range of about 90-120 degreeC. Moreover, you may perform manufacture of the said epoxy resin (A) and manufacture of an acidic radical containing (meth) acrylate resin continuously.

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

The said reaction catalyst can mention the compound similar to what is used in reaction of the said raw material epoxy resin (a1) and the said polyhydroxy compound (a2). It is preferable to use the addition amount of a catalyst in the range of 0.03-5 mass% with respect to the total mass of reaction raw material. When manufacturing the said epoxy resin (A) and manufacture of an acidic radical containing (meth) acrylate resin continuously, it is not necessary to add a catalyst newly and may add it suitably.

You may perform reaction in an organic solvent as needed. Examples of the organic solvent to be used include compounds similar to those used in the reaction between the raw material epoxy resin (a1) and the polyhydroxy compound (a2). Since the reaction efficiency becomes favorable for the usage-amount of the organic solvent, it is preferable to use in about 0.1-5 times the range with respect to the total mass of a reaction raw material.

Since the acid value of the acidic radical-containing (meth) acrylate resin of the present invention becomes an acidic radical-containing (meth) acrylate resin having excellent developability in addition to elongation and heat resistance in the cured product, the acid value of the acidic group-containing (meth) acrylate resin is preferably in the range of 40 to 90 mgKOH / g. . In addition, the acid value of an acidic radical containing (meth) acrylate resin in this invention is a value measured by the neutralization titration method of JISK0070 (1992).

Since the acidic radical containing (meth) acrylate resin of this invention has a polymeric (meth) acryloyl group in molecular structure, it can be used as curable resin composition by adding a photoinitiator, for example.

What is necessary is just to select and use the said photoinitiator suitably according to the kind etc. of the active energy ray to irradiate. Moreover, you may use together with photosensitizers, such as an amine compound, a urea compound, a sulfur compound, a phosphorus compound, a chlorine compound, and a nitrile compound. As a specific example of a photoinitiator, it is 1-hydroxy cyclohexyl phenyl- ketone, 2-benzyl-2- dimethylamino-1- (4-morpholinophenyl) -butanone- 1, 2- ( Alkylphenone type photoinitiators, such as dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; Acyl phosphine oxide photoinitiators such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; Intra-hydrogen hydrogen draw type | mold photoinitiators, such as a benzophenone compound, etc. are mentioned. These may be used independently, respectively and may use two or more types together.

Commercially available products of the photopolymerization initiator are, for example, "IRGACURE127", "IRGACURE184", "IRGACURE250", "IRGACURE270", "IRGACURE290", "IRGACURE369E", "IRGACURE379EG", "IRGACURE500", and "IRGACURE651" manufactured by BASF. IRGACURE754 "," IRGACURE819 "," IRGACURE907 "," IRGACURE1173 "," IRGACURE2959 "," IRGACURE MBF "," IRGACURE TPO "," IRGACURE OXE 01 "," IRGACURE OXE 02 "," OMNIRAD184250 "made by IGM RESINS "," OMNIRAD369 "," OMNIRAD369E "," OMNIRAD651 "," OMNIRAD907FF "," OMNIRAD1173 ", etc. are mentioned.

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

Curable resin composition of this invention may contain resin components other than the acidic radical containing (meth) acrylate resin of the said this invention. The resin component is, for example, in a resin obtained by reacting an epoxy resin such as a bisphenol-type epoxy resin or a novolak-type epoxy resin with (meth) acrylic acid, a dicarboxylic acid anhydride, an unsaturated monocarboxylic acid anhydride, and the like, if necessary. Resin which has a carboxy group and a (meth) acryloyl group, various (meth) acrylate monomers, etc. are mentioned.

The (meth) acrylate monomer may be, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl ( Aliphatic mono (meth) acrylate compounds such as meth) acrylate, 2-ethylhexyl (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 (meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy methoxyethyl (meth) acrylate, Aromatic mono (meth) acryl, such as 2-hydroxy-3- phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benzyl benzyl (meth) acrylate, and phenylphenoxyethyl (meth) acrylate Mono (meth) acrylate compounds such as late compounds; (Poly) oxyalkylene modified | denatured which introduce | transduced polyoxyalkylene chains, such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, a (poly) oxytetramethylene chain, in the molecular structure of the said various mono (meth) acrylate monomers Mono (meth) acrylate compounds; Lactone-modified mono (meth) acrylate compounds having a (poly) lactone structure introduced into the molecular structure of the various mono (meth) acrylate compounds;

Aliphatic di (meth), 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 ) Acrylate compound; 1,4-cyclohexane dimethanol di (meth) acrylate, norbornane di (meth) acrylate, norbornane dimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, tricyclodecane dimethanol Alicyclic di (meth) acrylate compounds such as di (meth) acrylate; Aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylate and bisphenol di (meth) acrylate; Polyoxyalkylene modified | denatured which introduce | transduced (poly) oxyalkylene chains, such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, a (poly) oxytetramethylene chain, in the molecular structure of the said various di (meth) acrylate compound Di (meth) acrylate compounds; Lactone-modified di (meth) acrylate compounds having a (poly) lactone structure introduced into the molecular structures of the various di (meth) acrylate compounds;

Aliphatic tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and glycerin tri (meth) acrylate; (Poly) oxyalkyl in which (poly) oxyalkylene chains such as (poly) oxyethylene chain, (poly) oxypropylene chain and (poly) oxytetramethylene chain are introduced into the molecular structure of the aliphatic tri (meth) acrylate compound Lene-modified tri (meth) acrylate compounds; Lactone-modified tri (meth) acrylate compounds having a (poly) lactone structure introduced into the molecular structure of the aliphatic tri (meth) acrylate compound;

Aliphatic poly (meth) acrylate compounds having four or more functional groups such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; Tetrafunctional or higher (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, (poly) oxytetramethylene chains, or the like, in the molecular structure of the aliphatic poly (meth) acrylate compound ) Oxyalkylene modified poly (meth) acrylate compound; The tetrafunctional or more lactone modified poly (meth) acrylate compound etc. which introduce | transduced the (poly) lactone structure in the molecular structure of the said aliphatic poly (meth) acrylate compound are mentioned.

Curable resin composition of this invention may contain the organic solvent for the purpose of coating viscosity adjustment, etc. The kind and amount of addition are suitably adjusted according to desired performance. Generally, it is used in 10-90 mass% with respect to the sum total of curable resin composition. As a specific example of the said solvent, 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; Aromatic solvents such as toluene and xylene; Alicyclic solvents such as cyclohexane and methylcyclohexane; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; Glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether and dialkylene glycol monoalkyl ether acetate. These may be used independently, respectively and may use two or more types together.

In addition, curable resin composition of this invention may contain various additives, such as an inorganic fine particle, a polymer fine particle, a pigment, an antifoamer, a viscosity modifier, a leveling agent, a flame retardant, a storage stabilizer.

The acidic radical-containing (meth) acrylate resin of this invention has the characteristic which was excellent in the balance of elongation and heat resistance in hardened | cured material. Generally, in order to reduce elongation of hardened | cured material, it is necessary to introduce a flexible structure in resin structure, but in this case, there exists a tendency for the heat resistance of hardened | cured material to fall remarkably. Since the acidic radical-containing (meth) acrylate resin of this invention has all these difficult performances at a high level, it has the performance which reverses the technical common sense so far. The acid group-containing (meth) acrylate resin of the present invention is a use of the excellent balance between elongation and heat resistance in the cured product. For example, the use of semiconductor device relations includes solder resists, interlayer insulating materials, It can be used as a package adhesive layer of a package material, an underfill material, a circuit element, etc., and an adhesive layer of an integrated circuit element and a circuit board. Moreover, as a use of the thin display relationship represented by LCD and OELD, it can be used suitably for a thin film transistor protective film, a liquid crystal color filter protective film, the pigment resist for color filters, the resist for black matrices, a spacer, etc.

Moreover, since the acidic radical containing (meth) acrylate resin of this invention is excellent also developability besides elongation and heat resistance in hardened | cured material, it can be used suitably for a soldering resist use. The resin material for soldering resists of this invention contains each component, such as a hardening | curing agent, a hardening accelerator, an organic solvent, in addition to the said acidic radical containing (meth) acrylate resin, a photoinitiator, and various additives.

The curing agent is not particularly limited as long as it has a functional group capable of reacting with a carboxyl group in the acid group-containing (meth) acrylate resin. Examples thereof include epoxy resins. The epoxy resin used here is a bisphenol type epoxy resin, a phenylene ether type epoxy resin, a naphthylene ether type epoxy resin, a biphenyl type epoxy resin, a triphenylmethane type epoxy resin, a phenol novolak type epoxy resin, for example. , Cresol novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol coaxial novolak type epoxy resin, naphthol-cresol coaxial novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aral A kill type epoxy resin, a dicyclopentadiene phenol addition reaction type epoxy resin, etc. are mentioned. These may be used independently, respectively and may use two or more types together. Among these epoxy resins, because of excellent heat resistance in the cured product, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a bisphenol novolak type epoxy resin, a naphthol novolak type epoxy resin, and a naphthol-phenol coaxial novolak type Novolak-type epoxy resins, such as an epoxy resin and a naphthol-cresol coaxial novolak-type epoxy resin, are preferable, and it is especially preferable that a softening point is 50-120 degreeC.

The said hardening accelerator accelerates hardening reaction of the said hardening | curing agent, and when using an epoxy resin as said hardening | curing agent, a phosphorus compound, tertiary amine, imidazole, organic acid metal salt, Lewis acid, amine complex salt, etc. are mentioned. . These may be used independently, respectively and may use two or more types together. 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 agents, for example.

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, Methoxy propanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and the like.

In the method of obtaining a resist member using the resin material for soldering resists of this invention, the said resin material for soldering resists is apply | coated on a base material, for example, carrying out the volatilization drying of the organic solvent in the temperature range of about 60-100 degreeC. Then, the method of exposing to an ultraviolet-ray, an electron beam, etc. through the photomask in which the desired pattern was formed, developing an unexposed part with aqueous alkali solution, and heat-hardening in the temperature range of about 140-180 degreeC is mentioned further.

(Example)

Below, an Example and a comparative example are given and this invention is demonstrated in detail.

Content of each component in an epoxy resin (a1) was computed from the area ratio of the GPC chart figure measured on the following conditions.

Measuring apparatus: "HLC-8320 GPC" manufactured by Tosoh Corp.

Column: Guard column "HXL-L" made by Tosoh Corp.

    `` TSK-GEL G2000HXL '' made by + Toso Corporation

    `` TSK-GEL G2000HXL '' made by + Toso Corporation

    `` TSK-GEL G3000HXL '' made by + Toso Corporation

    `` TSK-GEL G4000HXL '' made by + Toso Corporation

Detector: RI (Differential Refractometer)

Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corp.

Measurement condition: column temperature 40 ℃

            Developing solvent tetrahydrofuran

            Flow rate 1.0ml / min

Standard: Based on the measurement manual of "GPC Workstation EcoSEC-WorkStation", the following monodisperse polystyrene whose molecular weight is known was used.

 (Use Polystyrene)

  "A-500" made by Toso Corporation

  "A-1000" made by Toso Corporation

  "A-2500" made by Toso Corporation

  "A-5000" made by Toso Corporation

  "F-1" made by Toso Corporation

  "F-2" made by Toso Corporation

  "F-4" made by Toso Corporation

  "F-10" made by Toso Corporation

  "F-20" made by Toso Corporation

  "F-40" made by Toso Corporation

  "F-80" made by Toso Corporation

  "F-128" made by Toso Corporation

 Sample: 1.0 mass% of tetrahydrofuran solution filtered by micro filter in terms of resin solid content (50 μl)

MS data of an epoxy resin (a1) and C13NMR were measured by the following apparatus.

MS: Nippon Denshi Corporation double converging mass spectrometer AX505H (FD505H)

NMR: NMR GSX270 made by Nippon Denshi Corporation

In the Example of this application, the acid value of an acidic radical containing (meth) acrylate resin was measured by the neutralization titration method of JISK0070 (1992).

Preparation Example 1 Preparation of Epoxy Resin (a1)

240 g of 2,7-dihydroxynaphthalene, 85 g of 37 mass% formaldehyde aqueous solution, 376 g of isopropyl alcohol, and 88 g of potassium hydroxide aqueous solution were put into the flask equipped with the thermometer, the dropping funnel, the cooling tube, the sorting tube, and the stirrer. . Stirring was started, blowing in nitrogen, and it heated to 75 degreeC and stirred for 2 hours. 108 g of 1st sodium phosphates were added and neutralized after completion | finish of reaction. Isopropyl alcohol was removed under reduced pressure, and 480 g of methyl isobutyl ketone was added. After 200 g of water was added and the process of washing with water was repeated three times, methyl isobutyl ketone was removed under heat and reduced pressure to obtain a hydroxyl equivalent of 245 g of a phenol resin intermediate of 84 g / equivalent.

A nitrogen gas purge was conducted to a flask equipped with a thermometer, a cooling tube, and a stirrer while dissolving 84 g of the phenol resin intermediate, 463 g of epichlorohydrin, and 53 g of normal butanol. After heating to 50 ° C., 220 g of 20% aqueous sodium hydroxide aqueous solution was added over 3 hours, and further reacted for 1 hour. After completion | finish of reaction, it heated to 150 degreeC and distilled off unreacted epichlorohydrin under reduced pressure conditions. To the obtained crude product, 300 g of methyl isobutyl ketone and 50 g of normal butanol were added and dissolved. Furthermore, 15 g of 10 mass% sodium hydroxide aqueous solution was added, and it reacted at 80 degreeC for 2 hours. After washing with water until the pH of the washing | cleaning liquid became neutral, the inside of the system was azeotropically dehydrated. The solvent was distilled off under reduced pressure after microfiltration, and 126 g of epoxy resins (a1) were obtained. The softening point of the epoxy resin (a1) was 9.0 dPa · s and the epoxy equivalent was 174 g / equivalent at 95 ° C (B & R method), melt viscosity (measuring method: ICI viscometer method, measuring temperature: 150 ° C). The peak which shows presence of a carbonyl group in 203 ppm vicinity was confirmed by the C13NMR chart. Moreover, the peak of 512 which shows the presence of the compound represented by the following structural formula (x1) in the MS spectrum, and the peak of 556 which shows the presence of the compound represented by (x2) were confirmed. The epoxy resin (a1) contained 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 Preparation of Acid Group-containing (meth) acrylate Resin (1)

105 g of diethylene glycol monomethyl ether acetate, 190 g of the epoxy resin (a1) obtained above, and 5 g of 2,7-dihydroxynaphthalene were added and dissolved in a flask equipped with a thermometer, a stirrer, and a reflux condenser. 0.7 g of dibutylhydroxytoluene and 1.3 g of triphenylphosphines were added, and it was made to react at 150 degreeC for 2 hours in nitrogen atmosphere. 0.1 g of metoquinone and 74 g of acrylic acid were added, and it was made to react at 120 degreeC for 10 hours, blowing in air. 105 g of diethylene glycol monomethyl ether acetate and 73 g of tetrahydrophthalic anhydride were added, and it was made to react at 110 degreeC for 5 hours, and the acidic radical containing (meth) acrylate resin (1) was obtained. Solid content acid value of the acidic radical containing (meth) acrylate resin (1) was 80 mgKOH / g. The GPC chart of the acidic radical containing (meth) acrylate resin (1) is shown in FIG.

Example 2 Preparation of Acid-Containing (meth) acrylate Resin (2)

105 g of diethylene glycol monomethyl ether acetate, 190 g of the epoxy resin (a1) obtained above, and 5 g of 2,7-dihydroxynaphthalene were added and dissolved in a flask equipped with a thermometer, a stirrer, and a reflux condenser. 0.7 g of dibutylhydroxytoluene and 1.3 g of triphenylphosphines were added, and it was made to react at 150 degreeC for 2 hours in nitrogen atmosphere. 0.1 g of metoquinone and 74 g of acrylic acid were added, and it was made to react at 120 degreeC for 10 hours, blowing in air. 87 g of diethylene glycol monomethyl ether acetates and 44 g of succinic anhydride were added, and it reacted at 110 degreeC for 5 hours, and obtained the acidic radical containing (meth) acrylate resin (2). Solid content acid value of the acidic radical containing (meth) acrylate resin (2) was 80 mgKOH / g.

Comparative Production Example 1 Preparation of Acid Group-containing (meth) acrylate Resin (1 ')

To 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-glycidyloxynaphthyl) methane (DIC Corporation, "EPICLON HP- 4700 and 162 g of epoxy equivalents (162 g / equivalent) were added and dissolved. 0.6 g of dibutylhydroxytoluene and 0.1 g of metoquinone, 72 g of acrylic acid, and 1.2 g of triphenylphosphine were added as a thermal polymerization inhibitor, and reacted at 120 degreeC for 10 hours, blowing air. 95 g of diethylene glycol monomethyl ether acetate and 64 g of tetrahydrophthalic anhydride were added, and it was made to react at 110 degreeC for 5 hours, and the acidic radical containing (meth) acrylate resin (1 ') was obtained. Solid content acid value of acidic radical containing (meth) acrylate resin (1 ') was 80 mgKOH / g.

Examples 3 and 4 and Comparative Example 1

Curable resin composition was prepared in the following way, and various evaluation tests were done. The results are shown in Table 1.

◆ Heat Resistance of Hardened Materials and Evaluation of Elongation

Preparation of curable resin composition

100 g of acid-containing (meth) acrylate resins obtained before, 24 g of "EPICLON N-680" (cresol novolak-type epoxy resin) made by DIC Corporation, "irgacure907" made by BASF Corporation [2-methyl-1- (4 -Methylthiophenyl) -2-morpholinopropan-1-one] 5 g, "IRGACURE TPO" (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) 3 g made from BASF Corporation, diethylene glycol monomethyl ether 13 g of acetate was blended to obtain a curable resin composition.

Preparation of hard goods

Curable resin composition was apply | coated on the glass base material with a 50 micrometer applicator, and it dried at 80 degreeC for 30 minutes. After irradiating 1000 mJ / cm <2> ultraviolet-rays using the metal halide lamp, it heated at 160 degreeC for 1 hour, peeled the hardened | cured material from the glass base material, and obtained hardened | cured material.

Evaluation of the heat resistance of the hardened material

A 6 mm x 40 mm test piece was cut out from the cured product, and the elastic modulus was changed using a viscoelasticity measuring device (DMA: Solid viscoelasticity measuring device "RSAII" manufactured by Leo Matrix Corporation, Tensile method: frequency 1 Hz, temperature increase rate 3 ° C / min). The temperature at which the maximum (tanδ change rate is the largest) was evaluated as the glass transition temperature (Tg).

Evaluation of elongation of hardened goods

The test piece of 10 mm x 80 mm was cut out from hardened | cured material, and elongation was measured and evaluated on condition of the following using the tensile test apparatus ("The all-round testing machine Autograph AG-IS" made by Shimadzu Corporation).

Temperature 23 degrees Celsius, humidity 50%, distance between mark lines 20mm, distance between points 20mm, tensile rate 10mm / min

◆ Dryability, light sensitivity, evaluation of drying control width

Preparation of curable resin composition

100 g of acid group-containing (meth) acrylate resins obtained before, "EPICLON N-680" (cresol novolak-type epoxy resin) made by DIC Corporation, "Lumicure DPA-600T" made by Toagosei Corporation (Dipenta) 10 g of compositions containing erythritol pentaacrylate and dipentaerythritol hexaacrylate in molar ratio 40/60, "Irgacure907" by BASF Corporation [2-methyl-1- (4-methylthiophenyl) -2- Morpholinopropan-1-one] 5 g, "IRGACURE TPO" (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) 3 g made from BASF Corporation, 13 g of diethylene glycol monomethyl ether acetate, phthalocyanine green 0.65 as a pigment g was blended and kneaded with a roll mill to obtain a curable resin composition.

Fast evaluation

Curable resin composition was apply | coated on the glass base material with a 50 micrometer applicator, and it dried at 80 degreeC for 30 minutes. A polyethylene terephthalate (PET) film was placed on the surface of the coating film, and a weight of 50 g was left to stand for 10 seconds. Then, when the polyethylene terephthalate (PET) film was lifted, no sticking occurred. It evaluated as B.

Measurement of light sensitivity

Curable resin composition was apply | coated on the glass base material with a 50 micrometer applicator, and it dried at 80 degreeC for 30 minutes. Next, the ultraviolet-ray of 1000mJ / cm <2> was irradiated using the metal halide lamp via step tablet No. 2 made by Kodak Corporation. This was developed for 180 second with 1 mass% sodium carbonate aqueous solution, and the remaining number of stages evaluated. The higher the remaining number, the higher the photosensitivity.

Measurement of dry control width

The curable resin composition was apply | coated on the glass base material by the 50 micrometer applicator, and the sample whose drying time in 80 degreeC is 30 minutes, 40 minutes, 50 minutes, and 60 minutes respectively was created. These were developed for 180 seconds with a 1 mass% sodium carbonate aqueous solution, and the 80 degreeC drying time of the sample in which no residue remained was evaluated as drying control width. The longer the drying control range, the better the alkali developability.

TABLE 1

Claims (9)

As an acidic radical containing (meth) acrylate resin which makes an epoxy resin (A), unsaturated monocarboxylic acid or its derivative (B), and polycarboxylic acid anhydride (C) an essential reaction raw material, the said epoxy resin (A) is bis ( An acidic radical containing (meth) acrylate resin which is a reaction product of the raw material epoxy resin (a1) which makes polyglycidyl ether of the hydroxy naphthyl) alkane compound (p1) an essential component, and a polyhydroxy compound (a2). The method of claim 1,
The bis (hydroxynaphthyl) alkane compound (p1) is represented by the following structural formula (1)

[Wherein, R ¹ is each independently an aliphatic hydrocarbon group, an alkoxy group or a halogen atom, and R ² is an alkylene group. k is 1 or 2, l is 0 or an integer of 1 to 6]
Acid group-containing (meth) acrylate resin which is a compound represented by these. The method of claim 1,
Acid-group containing (meth) acrylate resin whose said polyhydroxy compound (a2) is an aromatic dihydroxy compound. The method of claim 1,
In addition to the polyglycidyl ether of the said bis (hydroxynaphthyl) alkane compound (p1), the said raw material epoxy resin (a1) has following structural formula (2)

[Wherein, R ¹ is each independently an aliphatic hydrocarbon group, an alkoxy group or a halogen atom, and R ² is an alkylene group. k is 1 or 2, n is 0 or 1, p is 0 or an integer of 1 to 5, q is 0 or an integer of 1 to 6]
Acid-group containing (meth) acrylate resin containing the polyglycidyl ether of compound (p2) represented by these. Curable resin composition containing the acidic radical containing (meth) acrylate resin of Claim 1, and a photoinitiator. Hardened | cured material of curable resin composition of Claim 5. The insulating material which consists of curable resin composition of Claim 5. The resin material for soldering resists which consists of curable resin composition of Claim 5. The resist member which uses the resin material for soldering resists of Claim 8.

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