JP6402968B2 - (Meth) acryloyl group-containing resin, method for producing (meth) acryloyl group-containing resin, curable resin material, cured product thereof, and resist material - Google Patents

Description

  The present invention relates to a (meth) acryloyl group-containing resin excellent in any of flame retardancy, heat resistance, hardness and electrical reliability in a cured product, a method for producing the same, a curable resin material, a cured product thereof, and a resist material.

  In recent years, the density of printed wiring boards has increased, the wiring has been increased, and the surface mounting of components has progressed.Accordingly, it is possible to form patterns with higher accuracy, as well as flame resistance, heat resistance, and hardness. There is a demand for the development of excellent resist materials. Examples of ultra fine patterning methods having a line width of 20 nm or less include nanoimprint methods, which are roughly classified into thermal nanoimprint methods and optical nanoimprint methods. Of these, the optical nanoimprint method, in which the composition is photocured by light irradiation, does not require heating of the mold material for pattern transfer during pressing, and imprinting at room temperature is possible. Has been.

  An alkali-developable acrylate group-containing resin obtained by reacting an acrylic ester of a phenol novolac type epoxy resin with tetrahydrophthalic anhydride is known as a photocurable resin for resist materials (see Patent Document 1). Such an alkali-developable acrylate group-containing resin is excellent in wet heat resistance and adhesion to a substrate in a cured product, but has sufficient performance such as sensitivity and developability, flame retardancy and hardness of the cured product, etc. Instead, development of a resin material having these performances at a high level has been demanded.

JP-A-8-12258

  Therefore, the problem to be solved by the present invention is a (meth) acryloyl group-containing resin excellent in any of flame retardancy, heat resistance, hardness and electrical reliability in a cured product, a method for producing the same, a curable resin material and the The object is to provide a cured product and a resist material.

  As a result of intensive studies to solve the above problems, the present inventors have found that a (meth) acryloyl group-containing resin obtained by acrylated an epoxy group of a polyarylene ether type epoxy resin having a naphthalene skeleton is flame retardant in a cured product. The present invention was completed by finding out that it was excellent in all of heat resistance, hardness and electrical reliability.

  That is, the present invention has a polyarylene ether structure (X), at least one of aromatic nuclei in the polyarylene ether structure (X) has a naphthalene skeleton, and the polyarylene ether structure (X ) At least one of the aromatic nuclei has the following structural formula (1-1) or (1-2) on the aromatic nuclei:

（式中Ｒ^１は水素原子またはメチル基を表す。）
で表される構造部位（Ｙ）を有することを特徴とする（メタ）アクリロイル基含有樹脂に関する。

(In the formula, R ¹ represents a hydrogen atom or a methyl group.)
And a (meth) acryloyl group-containing resin characterized by having a structural moiety (Y) represented by:

  The present invention further provides a polyarylene ether intermediate (α) obtained by reacting an aromatic dihydroxy compound and an aralkylating agent under an acid catalyst condition, and reacting this with an epihalohydrin to obtain an epoxy resin intermediate (β). The present invention further relates to a method for producing a (meth) acryloyl group-containing resin, which is further reacted with a (meth) acrylic acid derivative.

  The present invention further comprises reacting an aromatic dihydroxy compound under alkaline catalyst conditions to obtain a polyarylene ether intermediate (γ), and reacting this with an epihalohydrin to obtain an epoxy resin intermediate (ε), The present invention relates to a method for producing a (meth) acryloyl group-containing resin, characterized by reacting with a (meth) acrylic acid derivative.

  The present invention further relates to a curable resin material containing the (meth) acryloyl group-containing resin as an essential component.

  The present invention further relates to a cured product obtained by curing the curable resin material.

  The present invention further relates to a resist material containing the (meth) acryloyl group-containing resin and an alkali developable resin.

  The present invention further relates to a resist pattern made of the resist material.

  According to the present invention, a (meth) acryloyl group-containing resin excellent in any of flame retardancy, heat resistance, hardness, and electrical reliability in a cured product and a production method thereof, a curable resin material, a cured product thereof, and a resist material. Can be provided.

1 is a GPC chart of the polyarylene ether intermediate (α) obtained in Production Example 1. FIG. FIG. 2 is an FD-MS spectrum of the polyarylene ether intermediate (α) obtained in Production Example 1. FIG. 3 is an FD-MS spectrum of the trimethylsilylated product of the polyarylene ether intermediate (α) obtained in Production Example 1. FIG. 4 is a GPC chart of the polyarylene ether intermediate (γ) obtained in Production Example 2. FIG. 5 is an FT-IR chart of the polyarylene ether intermediate (γ) obtained in Production Example 2. 6 is an FD-MS spectrum of the polyarylene ether intermediate (γ) obtained in Production Example 2. FIG. FIG. 7 is an FD-MS spectrum of the trimethylsilylated polyarylene ether intermediate (γ) obtained in Production Example 1. FIG. 8 is a GPC chart of the (meth) acryloyl group-containing resin (1) obtained in Example 1.

Hereinafter, the present invention will be described in detail.
The (meth) acryloyl group-containing resin of the present invention has a polyarylene ether structure (X), at least one of the aromatic nuclei in the polyarylene ether structure (X) has a naphthalene skeleton, and At least one of the aromatic nuclei in the polyarylene ether structure (X) has the following structural formula (1-1) or (1-2) on the aromatic nuclei.

（式中Ｒ^１は水素原子またはメチル基を表す。）
で表される構造部位（Ｙ）を有することを特徴とする。

(In the formula, R ¹ represents a hydrogen atom or a methyl group.)
It has the structure site | part (Y) represented by these, It is characterized by the above-mentioned.

  In the (meth) acryloyl group-containing resin of the present invention, the polyarylene ether structure (X) is one in which at least one of the aromatic nuclei has a naphthalene skeleton, and a part of the aromatic nuclei has a phenyl skeleton. Also good. A resin having such a polyarylene ether structure (X) has a very high aromatic ring concentration and is easy to form a char during combustion, and thus has excellent heat resistance, hardness and flame retardancy in a cured product. Has characteristics.

  Especially, since it is further excellent in the flame retardance and heat resistance in hardened | cured material, it is preferable that 50 mol% or more of the aromatic nucleus in polyarylene ether structure (X) is what has a naphthalene skeleton, and polyarylene ether structure ( X) is preferably a polynaphthylene ether structure.

  In the (meth) acryloyl group-containing resin of the present invention, the (meth) acryloyl group-containing structural portion (Y) represented by the structure (1-1) or (1-2) is the polyarylene ether structure (X). It may be bonded to any of the aromatic nuclei. Above all, since it becomes a (meth) acryloyl group-containing resin that is excellent in sensitivity and developability, and is excellent in flame retardancy and heat resistance in a cured product, on the aromatic nucleus located at both ends of the polyarylene ether structure (X) It is preferable to have the structural site (Y).

  Therefore, the (meth) acryloyl group-containing resin of the present invention has the following structural formula (2).

［式中Ａｒは芳香核を表し、Ｙは下記構造式（１−１）又は（１−２）

[In the formula, Ar represents an aromatic nucleus, and Y represents the following structural formula (1-1) or (1-2).

（式中Ｒ^１は水素原子またはメチル基を表す。）
で表される構造部位（Ｙ）であり、Ｒ^２はそれぞれ独立に水素原子、アルキル基、アリール基、アラルキル基、下記構造式（３）

(In the formula, R ¹ represents a hydrogen atom or a methyl group.)
Wherein R ² is independently a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or the following structural formula (3):

｛式中Ａｒは芳香核を表し、Ｙは前記構造式（１−１）又は（１−２）で表される構造部位（Ｙ）であり、Ｒ^３はそれぞれ独立に水素原子、アルキル基、アリール基、アラルキル基を表し、ｍは１又は２である。｝
で表される構造部位の何れかであり、ｍは１又は２、ｎは１〜４の整数である。］
で表される分子構造を有するものが好ましく、下記構造式（４）

{Ar wherein represents an aromatic nucleus, Y is the structural formula (1-1) or (1-2) structure moiety represented by (Y), respectively ^{R 3} is independently a hydrogen atom, an alkyl group, Represents an aryl group or an aralkyl group, and m is 1 or 2. }
Wherein m is 1 or 2, and n is an integer of 1 to 4. ]
Those having a molecular structure represented by the following formula (4)

［式中Ｙは下記構造式（１−１）又は（１−２）

[Wherein Y represents the following structural formula (1-1) or (1-2)

（式中Ｒ^１は水素原子またはメチル基を表す。）
で表される構造部位（Ｙ）であり、Ｒ^４はそれぞれ独立に水素原子、アルキル基、アリール基、アラルキル基、下記構造式（５）

(In the formula, R ¹ represents a hydrogen atom or a methyl group.)
Wherein each R ⁴ independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or the following structural formula (5):

｛式中Ｙは前記構造式（１−１）又は（１−２）で表される構造部位（Ｙ）であり、Ｒ^５はそれぞれ独立に水素原子、アルキル基、アリール基、アラルキル基を表し、ｍは１又は２である。｝
で表される構造部位の何れかであり、ｍは１又は２、ｎは１〜４の整数である。］
で表される分子構造を有するものがより好ましい。

{Wherein Y is a structural moiety (Y) represented by the structural formula (1-1) or (1-2), and R ⁵ independently represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. , M is 1 or 2. }
Wherein m is 1 or 2, and n is an integer of 1 to 4. ]
Those having a molecular structure represented by

R ² in the structural formula (2) is independently a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, the following structural formula (3)

｛式中Ａｒは芳香核を表し、Ｙは前記構造式（１−１）又は（１−２）で表される構造部位（Ｙ）であり、Ｒ^３はそれぞれ独立に水素原子、アルキル基、アリール基、アラルキル基を表し、ｍは１又は２である。｝
で表される構造部位の何れかである。

{In the formula, Ar represents an aromatic nucleus; Y represents a structural moiety (Y) represented by the structural formula (1-1) or (1-2); and R ³ independently represents a hydrogen atom, an alkyl group, Represents an aryl group or an aralkyl group, and m is 1 or 2. }
Any one of the structural sites represented by

  Specific examples of the alkyl group, aryl group, aralkyl group include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group; phenyl group, tolyl group, xylyl group Aryl groups such as naphthyl group; benzyl group, phenylethyl group, phenylpropyl group, tolylmethyl group, tolylethyl group, tolylpropyl group, xylylmethyl group, xylylethyl group, xylylpropyl group, naphthylmethyl group, naphthylethyl group, naphthylpropyl group And an aralkyl group such as a group.

R ² in the structural formula (2) is a hydrogen atom, an aralkyl group, or a structural portion represented by the structural formula (3) because the cured product has excellent flame retardancy, heat resistance, and hardness. Is preferred.

R ³ in the structural formula (3) is a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and specific examples of the alkyl group, aryl group, and aralkyl group include those exemplified as the specific examples of R ^2. It is done. Among them, R ³ because of excellent flame retardant in the cured product is preferably a hydrogen atom.

R ⁴ in the structural formula (4) is independently a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, the following structural formula (5)

｛式中Ｙは前記構造式（１−１）又は（１−２）で表される構造部位（Ｙ）であり、Ｒ^５はそれぞれ独立に水素原子、アルキル基、アリール基、アラルキル基を表し、ｍは１又は２である。｝
で表される構造部位の何れかであり、アルキル基、アリール基、アラルキル基の具体例としては前記Ｒ^２の具体例として例示したものが挙げられる。中でも、硬化物における難燃性や耐熱性、硬度に優れることから、水素原子、アラルキル基、又は前記構造式（５）で表される構造部位であることが好ましい。

{Wherein Y is a structural moiety (Y) represented by the structural formula (1-1) or (1-2), and R ⁵ independently represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. , M is 1 or 2. }
Specific examples of the alkyl group, aryl group, and aralkyl group include those exemplified as the specific examples of R ² above. Especially, since it is excellent in the flame retardance in a hardened | cured material, heat resistance, and hardness, it is preferable that it is a hydrogen atom, an aralkyl group, or the structure site | part represented by said Structural formula (5).

R ⁵ in the structural formula (5) is a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and specific examples of the alkyl group, aryl group, and aralkyl group include those exemplified as the specific examples of R ^2. It is done. Among them, it is preferred that R ⁵ is a hydrogen atom because of excellent flame retardancy and electrical reliability in the cured product.

  The bonding position of the oxygen atom on the naphthalene skeleton in the structural formula (4) is, for example, 1,2-position, 1,4-position, 1,5-position, 1,6-position, 1,7-position. , 2,3-position, 2,6-position, 2,7-position, etc., it may be bonded to any carbon atom on the aromatic nucleus. Especially, since it is excellent in the flame retardance and heat resistance in hardened | cured material, it is preferable that it is 1,6-position or 2,7-position, and it is especially preferable that it is 2,7-position.

  Moreover, in the structural site represented by the structural formula (5), the bonding position of the substituent represented by Y on the naphthalene skeleton and the bond to the naphthalene skeleton in the structural formula (4) is, for example, 1,2-position, 1,4-position, 1,5-position, 1,6-position, 1,7-position, 2,3-position, 2,6-position, 2,7-position, etc., naphthalene It may be bonded to any carbon atom on the ring. Especially, since it is excellent in the flame retardance and heat resistance in hardened | cured material, it is preferable that it is 1,6-position or 2,7-position, and it is especially preferable that it is 2,7-position.

  N in the structural formula (2) and the structural formula (4) is an integer of 1 to 4. Among them, it is preferable to contain a resin component in which n is 1 or 2 because the viscosity is low and the cured product is excellent in both flame retardancy and moisture and solder resistance.

Further, all aromatic nuclei in the (meth) acryloyl group-containing resin represented by the structural formula (2) or the structural formula (4), that is, the aromatic nuclei constituting the polyarylene ether structure (X), and The sum of the aromatic nuclei represented by R ² , R ³ , R ⁴ , and R ⁵ in the structural formula (2) or (4) is excellent in sensitivity and developability, and flame retardancy and heat resistance in the cured product. From the standpoint of excellent hardness, it is preferably in the range of 4-12.

  In the (meth) acryloyl group-containing resin of the present invention, the content of the (meth) acryloyl group-containing structural portion represented by the structural formula (1-1) or (1-2), that is, the (meth) acryloyl group equivalent is It is preferably in the range of 200 to 1000 g / equivalent because it is excellent in curability and excellent in flame retardancy, heat resistance, hardness and electrical reliability in the cured product.

  The (meth) acryloyl group-containing resin of the present invention can be produced, for example, by the following method.

  Method 1: A polyarylene ether intermediate (α) obtained by reacting an aromatic dihydroxy compound and an aralkylating agent under an acid catalyst condition and an epihalohydrin are reacted to obtain an epoxy resin intermediate (β). Further, a method of reacting with a (meth) acrylic acid derivative.

  Method 2: A polyarylene ether intermediate (γ) obtained by reacting an aromatic dihydroxy compound under alkaline catalyst conditions and an epihalohydrin are reacted to obtain an epoxy resin intermediate (ε), which is further (meth) acrylic. A method of reacting with an acid derivative.

  The method 1 will be described. The aromatic dihydroxy compound used in Method 1 is, for example, 1,2-benzenediol, 1,3-benzenediol, 1,4-benzenediol or other dihydroxybenzene; 1,2-dihydroxynaphthalene, 1,4-dihydroxy And dihydroxynaphthalene such as naphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, etc. It is done. These may be used alone or in combination of two or more. Among these, dihydroxynaphthalene is preferable because it is excellent in flame retardancy and heat resistance in the cured product, 1,6-dihydroxynaphthalene or 2,7-dihydroxynaphthalene is more preferable, and 2,7-dihydroxynaphthalene is particularly preferable.

  Examples of the aralkylating agent used in Method 1 include benzyl chloride, benzyl bromide, benzyl iodide, o-methylbenzyl chloride, m-methylbenzyl chloride, p-methylbenzyl chloride, p-ethylbenzyl chloride, p-isopropylbenzyl. Chloride, p-tert-butylbenzyl chloride, p-phenylbenzyl chloride, 5-chloromethylacenaphthylene, 2-naphthylmethyl chloride, 1-chloromethyl-2-naphthalene and their nuclear substituted isomers, α-methylbenzyl Chlorides and halide compounds such as α, α-dimethylbenzyl chloride; benzyl methyl ether, o-methylbenzyl methyl ether, m-methylbenzyl methyl ether, p-methylbenzyl methyl ether ether compounds such as p-ethylbenzylmethyl ether and nucleosubstituted isomers thereof, benzylethyl ether, benzylpropyl ether, benzylisobutyl ether, benzyl n-butyl ether, p-methylbenzylmethyl ether and nucleosubstituted isomers thereof; benzyl alcohol , O-methylbenzyl alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol, p-ethylbenzyl alcohol, p-isopropylbenzyl alcohol, tert-butylbenzyl alcohol, p-phenylbenzyl alcohol, α-naphthylmethanol and these Nuclear substituted isomers, alcohol compounds such as α-methylbenzyl alcohol and α, α-dimethylbenzyl alcohol; styrene, o-methylstyrene, m-methylstyrene , Styrene compounds such as p-methylstyrene, α-methylstyrene, and β-methylstyrene. These may be used alone or in combination of two or more. Among these, benzyl chloride, benzyl bromide, and benzyl alcohol are preferable because a (meth) acryloyl group-containing resin excellent in flame retardancy and heat resistance in a cured product can be obtained.

  The reaction ratio between the aromatic dihydroxy compound and the aralkylating agent is such that a (meth) acryloyl group-containing resin excellent in flame retardancy and heat resistance in the cured product can be obtained, so that the molar ratio of both [dihydroxy compound / aralkylation Agent] is preferably in a ratio of 1.0 / 0.1 to 1.0 / 1.0.

  Examples of the acid catalyst used in Method 1 include inorganic acids such as phosphoric acid, sulfuric acid, and hydrochloric acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and organic acids such as fluoromethanesulfonic acid, aluminum chloride, and chloride. Examples include Friedel-Crafts catalysts such as zinc, stannic chloride, ferric chloride, and diethyl sulfate. These may be used alone or in combination of two or more.

  The amount of the acid catalyst used is preferably in the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the aromatic dihydroxy compound raw material in the case of an inorganic acid or an organic acid. Is preferably used in the range of 0.2 to 3.0 mol per mol of the aromatic dihydroxy compound raw material.

  The reaction of the aromatic dihydroxy compound and the aralkylating agent may be performed in an organic solvent as necessary. Examples of the organic solvent used herein include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, cellosolve, butyl carbitol, and the like. Examples thereof include carbitol solvents, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Each of these may be used alone, or two or more types of Hirono solvent may be used.

  The reaction between the aromatic dihydroxy compound and the aralkylating agent can be performed, for example, under a temperature condition of 100 to 180 ° C., and after completion of the reaction, the reaction system is filled with an alkali compound such as an alkali metal hydroxide. After neutralization, the water and organic solvent produced by the reaction can be dried under reduced pressure to obtain the polyarylene ether intermediate (α).

  The polyarylene ether intermediate (α) obtained in the first step of Method 1 has a (meth) acryloyl group which is excellent in sensitivity and developability and excellent in flame retardancy, heat resistance and hardness in a cured product. Since a resin is obtained, the hydroxyl equivalent is preferably in the range of 100 to 300 g / equivalent.

  Next, in the second step of Method 1, the polyarylene ether intermediate (α) and the epihalohydrin are reacted in the presence of a base catalyst to obtain an epoxy resin intermediate (β).

  Examples of the epihalohydrin used in the second step include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. Of these, epichlorohydrin is preferred because it is easily available industrially. When industrial production is performed, all of the epihalohydrins used for charging are new in the first batch of epoxy resin intermediate (β) production, but in the first batch and later, the epihalohydrin recovered from the crude reaction product is used. And new epihalohydrins corresponding to the amount consumed by the amount consumed in the reaction are preferably used in combination.

  The reaction rate of the polyarylene ether intermediate (α) and the epihalohydrin is such that the reaction proceeds efficiently, so that the epihalohydrin is 2 to 10 mol per 1 mol of the phenolic hydroxyl group in the polyarylene ether intermediate (α). It is preferable that the ratio be in the range.

  Examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. Among these, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity, and specific examples include sodium hydroxide and potassium hydroxide. These may be used in a solid state or may be used in the form of an aqueous solution of about 10 to 55% by mass.

  Since the reaction proceeds efficiently, the basic catalyst is added in an amount of 0.9 to 2.0 mol of the basic catalyst with respect to 1 mol of the phenolic hydroxyl group in the polyarylene ether intermediate (α). It is preferable to use in a ratio that falls within the range. In addition, the catalyst may be added all at once or dividedly.

  The reaction of the polyarylene ether intermediate (α) and epihalohydrin is usually carried out at a temperature range of 20 to 120 ° C. for about 0.5 to 10 hours. When an aqueous solution is used as the basic catalyst, an aqueous solution of the catalyst is continuously added to the reaction system, water and epihalohydrin are continuously distilled from the reaction mixture, and the distillate mixture is separated. A method of continuously returning the regenerated epihalohydrin to the reaction mixture again may be used.

  In addition, the reaction rate of the polyarylene ether intermediate (α) and epihalohydrin can be increased by carrying out the reaction in an organic solvent. Examples of the organic solvent used herein include ketone solvents such as acetone and methyl ethyl ketone, alcohol solvents such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, methyl cellosolve, ethyl cellosolve, and the like. And an aprotic polar solvent such as acetonitrile, dimethyl sulfoxide, dimethylformamide, and the like, and a cellosolve solvent, tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane. These organic solvents may be used alone or in combination of two or more kinds in order to adjust the polarity.

  After completion of the reaction in the second step, the reaction product is washed with water, and then unreacted epihalohydrin and the organic solvent are distilled off under heating and reduced pressure conditions to obtain an epoxy resin intermediate (β). Further, in order to reduce the amount of hydrolyzable halogen in the epoxy resin intermediate (β), the obtained epoxy resin intermediate (β) is dissolved again in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and the like. Additional reaction may be performed by adding an aqueous solution of an alkali metal hydroxide such as sodium or potassium hydroxide. At this time, in order to increase the reaction rate, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present. When using a phase transfer catalyst, it is preferable that it is a ratio from which a phase transfer catalyst will be 0.1-3.0 mass part with respect to 100 mass parts of epoxy resin intermediates ((beta)). After the completion of the additional reaction, the generated salt is removed by a method such as filtration or water washing, and a solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure conditions to obtain a higher purity epoxy resin intermediate ( β) can be obtained.

  In the third step of Method 1, the epoxy resin intermediate (β) and the (meth) acrylic acid derivative are reacted in the presence of an esterification catalyst such as triphenylphosphine to contain the desired (meth) acryloyl group. Obtain a resin.

  Examples of the (meth) acrylic acid derivative used here include acrylic acid, methacrylic acid, acrylic acid chloride, and methacrylic acid chloride. These may be used alone or in combination of two or more.

  The reaction ratio between the epoxy resin intermediate (β) and the (meth) acrylic acid derivative is such that the reaction proceeds efficiently, so the number of moles (p) of epoxy groups contained in the epoxy resin intermediate (β) The ratio [(p) / (q)] with the number of moles (q) of the (meth) acrylic acid derivative is preferably in a range of 1/1 to 1.1 / 1. Moreover, it is preferable that the reaction temperature at the time of making both react is the temperature range of 100-120 degreeC.

  Moreover, you may perform reaction with an epoxy resin intermediate body ((beta)) and a (meth) acrylic acid derivative in an organic solvent as needed. Examples of the organic solvent used herein include ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate, cellosolv solvents such as methyl cellosolve and ethyl cellosolve, and the like. Is mentioned. These organic solvents may be used alone or in combination of two or more kinds in order to adjust the polarity.

  When the (meth) acryloyl group-containing resin obtained by the method 1 is, for example, when 2,7-dihydroxynaphthalene is used as the aromatic dihydroxy compound and benzyl alcohol is used as the aralkylating agent, specifically, the following structural formula ( Examples thereof include those represented by any one of 6-1) to (6-18). In the formula, Bn represents a benzyl group, and Y represents the structural site (Y).

  In the method 1, when 1,6-dihydroxynaphthalene is used as the aromatic dihydroxy compound and benzyl alcohol is used as the aralkylating agent, the resulting (meth) acryloyl group-containing resin is specifically represented by the following structural formula ( 7-1) to any one of (7-20). In the formula, Bn represents a benzyl group, and Y represents the structural site (Y).

  Next, the method 2 will be described. The aromatic dihydroxy compound used in Method 2 is the same as that described in the description of Method 1.

  Examples of the alkali catalyst used in Method 1 include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, alkali metal carbonates such as potassium carbonate and sodium carbonate, and phosphorus compounds such as triphenylphosphine. . These may be used alone or in combination of two or more. Among these, alkali metal hydroxides are preferable because they are more excellent in reactivity.

  The amount of these alkali catalysts used is preferably in the range of 0.1 to 3.0 mol per 1 mol of the aromatic dihydroxy compound raw material.

  The condensation polymerization reaction of the aromatic dihydroxy compound may be performed in an organic solvent as necessary. Examples of the organic solvent used herein include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, cellosolve, and butyl carbitol. Examples thereof include carbitol solvents, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. These may be used alone or in combination of two or more.

  The polycondensation reaction of the aromatic dihydroxy compound can be performed, for example, at a temperature of 150 to 210 ° C. After the reaction is completed, the aqueous layer and the organic layer are separated, and then the organic solvent is dried from the organic layer under reduced pressure. Thus, a polyarylene ether intermediate (γ) can be obtained.

  The polyarylene ether intermediate (γ) obtained in the first step of Method 2 is excellent in sensitivity and developability, and is excellent in any of flame retardancy, heat resistance and hardness in a cured product. Since a resin is obtained, the hydroxyl equivalent is preferably in the range of 100 to 300 g / equivalent.

  Following the first step, the second step of obtaining an epoxy resin intermediate (ε) by reacting the polyarylene ether intermediate (γ) with epihalohydrin, the resulting epoxy resin intermediate (ε) and (meth) The third step of obtaining the desired (meth) acryloyl group-containing resin by reacting with an acrylic acid derivative can be carried out in the same manner as in Method 1.

  When the (meth) acryloyl group-containing resin obtained by the method 2 uses, for example, 2,7-dihydroxynaphthalene as an aromatic dihydroxy compound, specifically, the following structural formulas (8-1) to (8- 11) and the like. In the formula, Bn represents a benzyl group, and Y represents the structural site (Y).

  In the method 2, when 1,6-dihydroxynaphthalene is used as the aromatic dihydroxy compound, the resulting (meth) acryloyl group-containing resin is specifically represented by the following structural formulas (9-1) to (9- 8) and the like. In the formula, Bn represents a benzyl group, and Y represents the structural site (Y).

  The curable resin material of the present invention contains the (meth) acryloyl group-containing resin of the present invention as an essential component. In this invention, you may use together other radically polymerizable compounds other than the said (meth) acryloyl group containing resin as needed.

  Examples of the other radical polymerizable compounds include various epoxy (meth) acrylates and other (meth) acrylate compounds. In addition, the other radically polymerizable compound here is distinguished from an alkali-developable resin described later in that it does not have an acid group in the molecular structure and does not have alkali developability.

  Examples of the epoxy (meth) acrylate include those obtained by adding (meth) acrylic acid or a halide thereof to various polyglycidyl ether compounds. Examples of the various polyglycidyl ethers include hydroquinone, 2-methylhydroquinone, 1,4-benzenedimethanol, 3,3′-biphenol, 4,4′-biphenol, tetramethylbiphenol, biphenyl-3,3′-. Dimethanol, biphenyl-4,4′-dimethanol, bisphenol A, bisphenol B, bisphenol F, bisphenol S, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 2,6- Polyglycidyl ethers of aromatic polyols such as naphthalenediol, 2,7-naphthalenediol, naphthalene-2,6-dimethanol, 4,4 ′, 4 ″ -methylidynetrisphenol;

  Polyether modification obtained by ring-opening polymerization of the aromatic polyol and various cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. Polyglycidyl ethers of aromatic polyols;

  Polyglycidyl ether of a lactone-modified aromatic polyol obtained by polycondensation of the aromatic polyol with a lactone compound such as ε-caprolactone:

  A polyglycidyl ether of an aromatic ring-containing polyester polyol obtained by reacting an aliphatic dicarboxylic acid such as malonic acid, succinic acid, glutaric acid, adipic acid or pimelic acid with the aromatic polyol;

  Aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid and their anhydrides, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1 Aliphatic polyols such as 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, trimethylolethane, trimethylolpropane, glycerin, etc. A polyglycidyl ether of an aromatic ring-containing polyester polyol obtained by reacting with an aliphatic polyol of

  Bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol B type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type novolak resin; Co-condensed novolac type epoxy resin, cycloaliphatic epoxy resin, trisphenolmethane type epoxy resin, rubber-modified epoxy resin, tris (2,3-epoxypropyl) isocyanurate, diphenyldiglycidyl ether, tetramethyldiphenyldiglycidyl ether, oxazolidone Such as polyglycidyl ether of polyaddition reaction product of unsaturated cycloaliphatic compound such as epoxy resin containing ring, dicyclopentadiene and phenols Such as epoxy resin and the like. These may be used alone or in combination of two or more.

  Examples of the other (meth) acrylate compounds include n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, glycidyl (meth) acrylate, morpholine ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono ( Acrylate), triethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (Meth) acrylate, 2-butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, ethoxy polyethylene glycol ( (Meth) acrylate, 4-nonylphenoxyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolact Modified tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, cyclohexylethyl ( (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenylbenzyl (meth) acrylate, Monofunctional (meth) acrylate compounds such as phenylphenoxyethyl acrylate;

  Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tri Propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, tetrabutylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1 , 9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, di (meth) acrylate of bisphenol A ethylene oxide adduct, bisphenol Di (meth) acrylate of propylene oxide adduct of diol A, di (meth) acrylate of ethylene oxide adduct of bisphenol F, di (meth) acrylate of propylene oxide adduct of bisphenol F, dicyclopentanyl di (meth) Acrylate, glycerol di (meth) acrylate, neopentyl glycol hydroxypivalate ester di (meth) acrylate, caprolactone modified hydroxypivalate neopentyl glycol di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, hydropivalaldehyde modified Trimethylolpropane di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, bis [(meth) acryloylmethyl] biphenyl, etc. Di (meth) acrylate compound;

  Trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide adduct tri (meth) acrylate, trimethylolpropane propylene oxide adduct tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol tri ( Of (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane ethylene oxide adduct tetra (meth) acrylate, ditrimethylolpropane propylene oxide adduct Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Trifunctional or more (meth) acrylate compounds such like. These may be used alone or in combination of two or more.

  The blending ratio of the (meth) acryloyl group-containing resin and the other radical polymerizable compound in the curable resin material of the present invention is, for example, using the (meth) acryloyl group-containing resin of the present invention alone, or It is preferable to use the other radical polymerizable compound in an amount of 10 to 200 parts by mass with respect to 100 parts by mass of the (meth) acryloyl group-containing resin of the present invention.

  The curable resin material of the present invention can be made into a cured product by adding a polymerization initiator and irradiating an active energy ray or applying heat to cure.

  When the curable resin material of the present invention is irradiated with active energy rays and cured by radical polymerization, an intramolecular cleavage type photopolymerization initiator or a hydrogen abstraction type photopolymerization initiator is used as the polymerization initiator.

  Examples of the intramolecular cleavage type photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4 -Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-methyl-2-morpholino (4-thio Acetophenone-based compounds such as methylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 4,6-trimethylbenzoindiphenylphos Acylphosphine oxide compounds such as fin oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; 1,1′-azobisisobutyronitrile, 1,1′-azobiscyclohexanecarbonitrile, 2 -Azo compounds such as cyano-2-propylazoformamide; benzyl, methylphenylglyoxyester and the like.

  Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, Benzophenone compounds such as acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4- Thioxanthone compounds such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; Aminobenzophenone compounds such as Michler-ketone and 4,4′-diethylaminobenzophenone; 10-butyl 2-chloro-acridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, and the like.

  Among the above photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane -1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl- Acetophenone compounds such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone and benzophenone are preferred, and 1-hydroxycyclohexyl phenyl ketone is particularly preferred. These photopolymerization initiators can be used alone or in combination of two or more.

  0.01-20 mass parts is preferable with respect to 100 mass parts of curable resin materials of this invention, and, as for the usage-amount of the said photoinitiator, 0.1-15 mass% is more preferable, 0.5-10 masses Part is more preferred. In addition, when using the electron beam mentioned later as an active energy ray, a photoinitiator is unnecessary.

  Examples of the active energy rays used for curing the curable resin material of the present invention include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Examples of energy sources or curing devices that generate these active energy rays include germicidal lamps, ultraviolet lamps (black lights), carbon arcs, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, Examples thereof include an electrode lamp, a metal halide lamp, an ArF excimer laser, an ultraviolet LED, an ultraviolet ray using natural light as a light source, or an electron beam by a scanning type or curtain type electron beam accelerator.

  In addition, when the curable resin material of the present invention is cured by thermal radical polymerization, a thermal radical polymerization initiator is used. Examples of the thermal radical polymerization initiator include benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 3,3,5-trimethylhexanoyl peroxide, di-2-ethylhexyl peroxydicarbonate, and methyl ethyl ketone. Peroxide, t-butyl peroxyphthalate, t-butyl peroxybenzoate, di-t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-hexanoate, t-butyl peroxy Organic peroxides such as 3,3,5-trimethylhexanoate; 1,1′-azobisisobutyronitrile, 1,1′-azobiscyclohexanecarbonitrile, 2-cyano-2-propylazoformamide And azo compounds. Among these thermal radical polymerization initiators, benzoyl peroxide and 1,1'-azobisisobutyronitrile are preferable. Moreover, these thermal radical polymerization initiators can be used alone or in combination of two or more.

  0.01-20 mass parts is preferable with respect to 100 mass parts of curable resin materials of this invention, and, as for the usage-amount of the said thermal radical polymerization initiator, 0.1-15 mass% is more preferable, 0.5-10 Part by mass is more preferable.

  The curable resin material of the present invention may contain an organic solvent depending on the application. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbon compounds such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, di Glycol ether compounds such as propylene glycol monoethyl ether and dipropylene glycol diethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate; ethanol, propanol, ethylene glycol, propylene glycol Alcohols such as octane, decane, etc .; petroleum ether, petroleum Sa, hydrogenated petroleum naphtha, organic solvents such as petroleum-based solvents such as solvent naphtha. These may be used singly or as a mixed solvent of two or more kinds.

  Although the compounding quantity of the said organic solvent changes with uses etc., it is preferable to use in the ratio from which resin solid content in curable resin material will be 20-80 mass%.

  When the curable resin material of the present invention is used for resist material applications, an alkali developable resin, an epoxy resin, or the like is blended together with the (meth) acryloyl group-containing resin of the present invention.

  Examples of the alkali developable resin include a reaction product of a (meth) acrylic acid ester of an epoxy resin and a polybasic acid anhydride. Examples of the (meth) acrylic acid ester of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol B type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; phenol novolac type epoxy resin, Cresol novolac type epoxy resin, bisphenol type novolak resin; Resorcin / cresol co-condensation novolak type epoxy resin, alicyclic epoxy resin, trisphenol methane type epoxy resin, rubber-modified epoxy resin, tris (2,3-epoxypropyl) isocyanurate Diphenyl diglycidyl ether, tetramethyl diphenyl diglycidyl ether, epoxy resin containing an oxazolidone ring, and unsaturated alicyclic compounds such as dicyclopentadiene Those polyaddition of epoxy groups in the epoxy resin polyglycidyl ether reactant (meth) acrylic acid (meth) acrylate of a phenol compound and the like. These may be used alone or in combination of two or more.

  On the other hand, the polybasic acid anhydride is, for example, maleic anhydride, succinic anhydride, itaconic anhydride, dodecyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyl Tetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride, 3 Aliphatic such as butenyl-5,6-dimethyltetrahydrophthalic anhydride, 3,6-endomethylene-tetrahydrophthalic anhydride, 7-methyl-3,6-endomethylenetetrahydrophthalic anhydride, benzophenone tetracarboxylic anhydride Acid anhydride; phthalic anhydride, tetrachlorophthalic anhydride, te Raburomo phthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, aromatic monoacid anhydride such as benzophenone tetracarboxylic acid anhydride. These may be used alone or in combination of two or more.

  Examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol B type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol Type novolak resin; resorcin / cresol co-condensation novolak type epoxy resin, alicyclic epoxy resin, trisphenolmethane type epoxy resin, rubber-modified epoxy resin, tris (2,3-epoxypropyl) isocyanurate, diphenyldiglycidyl ether, tetra Polyaddition reaction product of unsaturated alicyclic compounds such as methyldiphenyldiglycidyl ether, epoxy resin containing oxazolidone ring, dicyclopentadiene and phenols Polyglycidyl ether, and the like. These may be used alone or in combination of two or more.

  The blending amount of the alkali-developable resin is preferably used in the range of 30 to 500 parts by mass, and preferably in the range of 100 to 300 parts by mass with respect to 100 parts by mass of the (meth) acryloyl group-containing resin of the present invention. . Moreover, it is preferable to use the compounding quantity of the said epoxy resin in the range of 30-500 mass parts with respect to 100 mass parts of (meth) acryloyl group containing resin of this invention, and it is preferable to use it in the range of 100-300 mass parts. .

  The (meth) acryloyl group-containing resin of the present invention itself has a high flame retardancy, but when used for an application requiring high flame retardancy, a non-halogen flame retardant containing substantially no halogen atom is used. You may mix | blend.

  Examples of the non-halogen flame retardant include a phosphorus flame retardant, a nitrogen flame retardant, a silicone flame retardant, an inorganic flame retardant, an organic metal salt flame retardant, and the like. It is not intended to be used alone, and a plurality of the same type of flame retardants may be used, or different types of flame retardants may be used in combination.

  As the phosphorus flame retardant, either inorganic or organic can be used. Examples of the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide For example, a method of double coating with a resin may be used.

  The organic phosphorus compounds include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7- Examples thereof include cyclic organic phosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  For example, in the case where red phosphorus is used in 100 parts by mass of the curable resin material, the phosphorus-based flame retardant is preferably compounded in an amount of 0.1 to 2.0 parts by mass. When using, it is preferable to mix | blend in the range of 0.1-10.0 mass part, and it is more preferable to mix | blend in the range of 0.5-6.0 mass part.

  In addition, when using the phosphorous flame retardant, the phosphorous flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine and the like, for example, sulfuric acid such as guanylmelamine sulfate, melem sulfate, melam sulfate Examples thereof include aminotriazine compounds, aminotriazine-modified phenol resins, and aminotriazine-modified phenol resins that are further modified with tung oil, isomerized linseed oil, and the like.

  Examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The blending amount of the nitrogen-based flame retardant is preferably blended in the range of 0.05 to 10 parts by mass, for example, in the range of 0.1 to 5 parts by mass in 100 parts by mass of the curable resin material. Is more preferable.

  Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  It is preferable to mix | blend the compounding quantity of the said silicone type flame retardant in the range of 0.05-20 mass parts in 100 mass parts of curable resin materials, for example. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.

  Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide.

  Examples of the metal oxide include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, Examples thereof include chromium oxide, nickel oxide, copper oxide, and tungsten oxide.

  Examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

  Examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

  Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

Examples of the low-melting-point glass include Shipley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, and P ₂ O _5. Glassy compounds such as —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, and lead borosilicate Can be mentioned.

  The blending amount of the inorganic flame retardant is, for example, preferably in the range of 0.05 to 20 parts by mass and in the range of 0.5 to 15 parts by mass in 100 parts by mass of the curable resin material. Is more preferable.

  Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound. And the like.

  It is preferable to mix | blend the compounding quantity of the said organometallic salt type flame retardant in the range of 0.005-10 mass parts in 100 mass parts of curable resin materials, for example.

  The curable resin material of this invention can mix | blend an inorganic filler as needed. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 20% by mass or more with respect to the total mass of the curable resin material. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  In addition to the above, the curable resin material of the present invention may contain various compounding agents such as a silane coupling agent, a release agent, a pigment, and an emulsifier, if necessary.

  The curable resin material of the present invention is obtained by uniformly mixing the above-described components, and can be easily made into a cured product by heating. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  When the curable resin material of the present invention is used as a resin composition for resist inks, for example, a screen printing, curtain coating method, roll coating method, spin coating method, dip coating method or the like is applied to a printed substrate by 10 to 150 μm ( After coating to a thickness of (liquid film thickness), it is pre-dried at 60-90 ° C. for 15-90 minutes to volatilize volatile components such as organic solvents (the coating and pre-drying steps may be repeated several times to laminate). Then, a negative film of a desired mask pattern is adhered to the dried coating film, and exposure is performed by irradiating with ultraviolet rays from above (or the pattern may be directly exposed using laser light, etc. In this case, the mask pattern is The film in the non-exposed area is removed by developing with a dilute alkaline aqueous solution as a developer, and the film in the exposed part is photocured. By remaining without being removed, so it is possible to form a pattern. In this case, the dilute alkaline aqueous solution is generally 0.5 to 5% by mass of sodium carbonate aqueous solution or sodium hydroxide aqueous solution, but other alkaline solutions can also be used. Subsequently, a resist pattern excellent in various physical properties such as heat resistance, flame retardancy, hardness, and electrical characteristics can be obtained by thermosetting with a hot air dryer or the like at 130 to 160 ° C. for 20 to 90 minutes.

  The curable resin material of the present invention includes a resin composition for a solder resist ink of a circuit board such as a printed wiring board, an interlayer insulating layer, a liquid crystal color filter overcoat, a liquid crystal spacer, a color filter pigment resist, a black matrix, etc. In addition to resist materials, hard printed wiring board materials, resin compositions for flexible wiring boards, insulating materials for circuit boards such as interlayer insulating materials for build-up boards, semiconductor sealing materials, conductive pastes, build-up adhesive films, resins It can be used for various electronic materials such as casting materials and adhesives.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on mass unless otherwise specified. In addition, the softening point measurement, melting | fusing point measurement, GPC measurement, < ¹³ > C-NMR, MS spectrum, and IR were measured on condition of the following.

Softening point measurement method: compliant with JIS K7234.

Melting point measurement method: Conforms to ASTM D4287.

GPC: Measured under the following conditions.
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.

(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

13C-NMR: Measured with “JNM-ECA500” manufactured by JEOL Ltd.
Magnetic field strength: 500 MHz
Pulse width: 3.25 μsec
Integration count: 8000 times Solvent: DMSO-d6
Sample concentration: 30% by mass

FD-MS: Measured using “JMS-T100GC AccuTOF” manufactured by JEOL Ltd.
Measurement range: m / z = 4.00-2000.00
Rate of change: 51.2 mA / min
Final current value: 45 mA
Cathode voltage: -10 kV
Recording interval: 0.07 sec

IR: Measured by KBr method using “Nicolet iS10” manufactured by Thermo Fisher Scientific.

Production Example 1 Production of polyarylene ether intermediate (α) 160 g (1.0 mol) of 2,7-dihydroxynaphthalene and benzyl alcohol were added to a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube and a stirrer. 25 g (0.25 mol), 160 g of xylene and 2 g of paratoluenesulfonic acid monohydrate were charged and stirred at room temperature while blowing nitrogen. Next, the temperature was raised to 140 ° C., and the generated water was distilled out of the system, and at the same time, the distilled xylene was stirred for 4 hours while returning to the system. The temperature was further raised to 150 ° C., and the resulting water and xylene were stirred for 3 hours while distilling out of the system. After completion of the reaction, 2 g of 20% aqueous sodium hydroxide solution was added for neutralization, and then water and xylene were removed under reduced pressure to obtain 178 g of a brown solid polyarylene ether intermediate (α). The obtained polyarylene ether intermediate (α) had a hydroxyl group equivalent of 178 g / equivalent and a softening point of 130 ° C. FIG. 1 shows the GPC chart of the polyarylene ether intermediate (α), FIG. 2 shows the MALDI-MS spectrum, and FIG. 3 shows the MALDI-MS spectrum of the trimethylsilylated polyarylene ether intermediate (1).

From the molecular weight peaks in FIGS. 2 and 3, the presence of each compound of a to f was confirmed.
a. A peak (M ⁺ = 250) with one benzyl group (molecular weight Mw: 90) added to 2,7-dihydroxynaphthalene (Mw: 160) and a peak with two benzyl groups (molecular weight Mw: 90) added (M ⁺ = 340), the presence of a compound in which 1 mol of benzyl group was bonded to 1 mol of 2,7-dihydroxynaphthalene and a compound in which 2 mol of benzyl group was bonded to 1 mol of 2,7-dihydroxynaphthalene. confirmed.

b. Since a peak of 2,7-dihydroxynaphthalene dimer (M ⁺ = 302) and a peak (M ⁺ = 446) in which two trimethylsilyl groups (molecular weight Mw: 72) were added were observed, The presence of a dimer ether compound of 7-dihydroxynaphthalene was confirmed.

c. A peak of 2,7-dihydroxynaphthalene trimer (M ⁺ = 444), a peak obtained by adding two trimethylsilyl groups (molecular weight Mw: 72) (M ⁺ = 588), and a peak obtained by adding three trimethylsilyl groups Since (M ⁺ = 660) was observed, 1 mol of 2,7-dihydroxynaphthalene was added to 1 mol of 2,7-dihydroxynaphthalene trimer ether compound and 1 mol of 2,7-dihydroxynaphthalene dimer ether compound. The presence of a trimer compound having a structure formed by dehydration was confirmed.

d. A peak of 2,7-dihydroxynaphthalene tetramer (M ⁺ = 586), a peak obtained by adding two trimethylsilyl groups (molecular weight Mw: 72) to this (M ⁺ = 730), and a peak obtained by adding three trimethylsilyl groups Since (M ⁺ = 802) was observed, 1 mol of 2,7-dihydroxynaphthalene was added to 1 mol of 2,7-dihydroxynaphthalene tetramer ether compound and 2 mol of 2,7-dihydroxynaphthalene trimer ether compound. The presence of a tetramer compound having a structure formed by dehydration was confirmed.

e. Peak of 2,7-dihydroxynaphthalene pentamer (M ⁺ = 729), peak obtained by adding two trimethylsilyl groups (molecular weight Mw: 72) (M ⁺ = 873), peak obtained by adding three trimethylsilyl groups ( M ⁺ = 944) and a peak (M ⁺ = 1016) with four trimethylsilyl groups added, 2,7-dihydroxynaphthalene pentamer ether compound, 2,7-dihydroxynaphthalene tetramer ether 2 mol nucleus of 2,7-dihydroxynaphthalene per 1 mol of 2,7-dihydroxynaphthalene, 1 mol of 2,7-dihydroxynaphthalene is a pentamer compound formed by dehydration, and 1 mol of 2,7-dihydroxynaphthalene trimer ether compound The presence of a pentamer compound having a structure formed by dehydration was confirmed.

f. Since a peak in which one benzyl group (molecular weight Mw: 90) was added and a peak in which two benzyl groups (molecular weight Mw: 90) were added were observed in each of the compounds identified in b to e, b to The presence of 1 mol of a benzyl group and 1 mol of a compound bonded with 2 mol of each of the compounds identified in e was confirmed.

Production Example 2 Production of polyarylene ether intermediate (γ) A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was charged with 160 g (1.0 mol) of 2,7-dihydroxynaphthalene, The mixture was heated and melted at 200 ° C. with stirring while blowing nitrogen. After melting, 23 g (0.2 mol) of 48% aqueous potassium hydroxide solution was added, and water derived from the 48% aqueous potassium hydroxide solution and water produced were extracted using a fractionating tube, and then reacted for another 5 hours. . After completion of the reaction, 1000 g of methyl isobutyl ketone was added to the reaction system to dissolve the contents and transferred to a separatory funnel. After washing with water until the washing water showed neutrality, the solvent was removed from the organic layer under heating and reduced pressure to obtain 150 g of a brown solid polyarylene ether intermediate (γ). The obtained polyarylene ether intermediate (γ) had a hydroxyl group equivalent of 120 g / equivalent and a melting point of 179 ° C. The GPC chart of the polyarylene ether intermediate (γ) is shown in FIG. 4, the FT-IR chart is shown in FIG. 5, the MALDI-MS spectrum is shown in FIG. 6, and the MALDI-MS of the polyarylene ether intermediate (γ) is trimethylsilylated. The spectrum is shown in FIG.

From the GPC chart of FIG. 4, it was confirmed that the residual ratio of 2,7-dihydroxynaphthalene in the polyarylene ether intermediate (γ) was 64% in terms of area ratio by GPC.
From the FT-IR chart of FIG. 5, absorption (1250 cm ⁻¹ ) derived from aromatic ether was confirmed, confirming the formation of a polynaphthylene ether structure.
From the molecular weight peaks in FIG. 6 and FIG. 7, the presence of each compound of a to f below was confirmed.

a. A peak of 2,7-dihydroxynaphthalene trimer (M ⁺ = 444), a peak obtained by adding two trimethylsilyl groups (molecular weight Mw: 72) (M ⁺ = 588), and a peak obtained by adding three trimethylsilyl groups Since (M ⁺ = 660) was observed, 1 mol of 2,7-dihydroxynaphthalene was added to 1 mol of 2,7-dihydroxynaphthalene trimer ether compound and 1 mol of 2,7-dihydroxynaphthalene dimer ether compound. The presence of a trimer compound having a structure formed by dehydration was confirmed.

b. Peak of 2,7-dihydroxynaphthalene pentamer (M ⁺ = 728), peak obtained by adding 3 trimethylsilyl groups (molecular weight Mw: 72) to this (M ⁺ = 945), and peak obtained by adding 4 trimethylsilyl groups Since (M ⁺ = 1018) was observed, 1 mol of 2,7-dihydroxynaphthalene was added to 1 mol of 2,7-dihydroxynaphthalene pentamer ether compound and 1 mol of 2,7-dihydroxynaphthalene tetramer ether compound. The presence of a pentamer compound having a structure formed by the nuclear dehydration of 2 mol of 2,7-dihydroxynaphthalene per mole of 2,7-dihydroxynaphthalene trimer ether compound was confirmed. did.

Production Example 3 Production of Epoxy Resin Intermediate (β) 178 g of polyarylene ether intermediate (α) obtained in Production Example 1 while subjecting a flask equipped with a thermometer, a dropping funnel, a condenser tube, and a stirrer to nitrogen gas purge. (Hydroxyl group 1.0 mol), epichlorohydrin 463 g (5.0 mol), n-butanol 139 g, and tetraethylbenzylammonium chloride 2 g were charged and dissolved. The temperature was raised to 65 ° C., the pressure was reduced to an azeotropic pressure, and 90 g (1.1 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Thereafter, stirring was continued for 0.5 hours under the same conditions. During this time, the distillate distilled by azeotropic distillation was separated with a Dean-Stark trap, and the reaction was carried out while removing the aqueous layer and returning the oil layer into the reaction system. Subsequently, unreacted epichlorohydrin was distilled off under reduced pressure to obtain a crude epoxy resin. To the crude epoxy resin, 455 g of methyl isobutyl ketone and 137 g of n-butanol were added and dissolved, and further 10 g of 10% aqueous sodium hydroxide solution was added and reacted at 80 ° C. for 2 hours. After completion of the reaction, water washing with 150 g of water was repeated 3 times until the pH of the washing liquid became neutral. Next, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain 242 g of an epoxy resin intermediate (β). The epoxy equivalent of the obtained epoxy resin intermediate (β) was 292 g / eq.

Production Example 4 Production of Epoxy Resin Intermediate (ε) 178 g (1.0 mol of hydroxyl group) of polyarylene ether intermediate (α) of Production Example 3 was converted to 120 g of polyarylene ether intermediate (γ) (1.0 mol of hydroxyl group). An epoxy resin intermediate (ε) was obtained by the same operation as in Production Example 3 except that the change was made. The epoxy equivalent of the obtained epoxy resin intermediate (ε) was 197 g / eq.

Example 1 Production of (meth) acryloyl group-containing resin (1) The epoxy resin intermediate obtained in Production Example 3 while blowing air into a flask equipped with a thermometer, a cooling tube, an air introduction tube, and a stirrer ( β) 292 g (epoxy group 1.0 mol), ethylene glycol monoethyl ether acetate 196 g, acrylic acid 72 g (1.0 mol) and hydroquinone 0.18 g were charged, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. Next, 1.09 g of triphenylphosphine was charged and reacted at 120 ° C. for 6 hours to obtain a (meth) acryloyl group-containing resin (1) solution. The solid content of the obtained (meth) acryloyl group-containing resin (1) solution was 65% by mass, and the double bond equivalent of the solid calculated from the raw material charge ratio was 364 g / equivalent. FIG. 8 shows a GPC chart of the (meth) acryloyl group-containing resin (1).

Example 2 Production of (meth) acryloyl group-containing resin (2) The epoxy resin intermediate (β) of Example 1 was changed to 197 g of epoxy resin intermediate (ε) (1.0 mol of epoxy groups), and hydroquinone was changed to 0. A (meth) acryloyl group-containing resin (2) solution was obtained in the same manner as in Example 1, except that the amount of triphenylphosphine was changed to 0.81 g. The solid content of the obtained (meth) acryloyl group-containing resin (2) solution was 65% by mass, and the double bond equivalent of the solid calculated from the raw material charge ratio was 269 g / equivalent.

Example 3 Production of (meth) acryloyl group-containing resin (3) 72 g of acrylic acid in Example 1 was changed to 86 g (1.0 mol) of methacrylic acid, 0.19 g of hydroquinone and 1.13 g of triphenylphosphine. A (meth) acryloyl group-containing resin (3) solution was obtained in the same manner as in Example 1 except that the change was made. The solid content of the obtained (meth) acryloyl group-containing resin (3) solution was 65% by mass, and the double bond equivalent of the solid calculated from the raw material charge ratio was 378 g / equivalent.

Example 4 Synthesis of (meth) acryloyl group-containing resin (4) The epoxy resin intermediate of Example 1 was changed to 197 g of epoxy resin intermediate (ε) (1.0 mol of epoxy groups), and acrylic acid was 86 g of methacrylic acid. The (meth) acryloyl group-containing resin (4) solution was changed in the same manner as in Example 1 except that the hydroquinone was changed to 0.14 g and triphenylphosphine was changed to 0.85 g. Obtained. The solid content of the obtained (meth) acryloyl group-containing resin (4) solution was 65% by mass, and the double bond equivalent of the solid calculated from the raw material charge ratio was 283 g / equivalent.

Production of Alkali Developable Resin (1) Into a flask equipped with a thermometer, stirrer, dropping funnel and reflux condenser, 297 g of ethyl diglycol acetate was introduced, and cresol novolac epoxy resin (“Epiclon N” manufactured by DIC Corporation) was introduced. -680 "epoxy equivalent 210g / equivalent) 630g was added and dissolved by heating. Subsequently, 216 g of acrylic acid, 0.6 g of hydroquinone as a polymerization inhibitor, and 2.5 g of triphenylphosphine as a reaction catalyst were added, heated to 120 ° C., and reacted for about 12 hours. After cooling the reaction product to 80 ° C., 252 g of tetrahydrophthalic anhydride was added and reacted for about 6 hours. To this reaction solution, 297 g of Solvesso 150 was added to obtain an alkali developable resin (1) solution. The solid content of the alkali-developable resin (1) solution was 65% by mass, and the acid value of the solid content was 85 mgKOH / g.

Comparative Production Example 1 Production of (meth) acryloyl group-containing resin (1 ′) The epoxy resin intermediate (β) of Example 1 was treated with an ortho-cresol novolac type epoxy resin (“Epiclon N-680” manufactured by DIC Corporation, epoxy equivalent 210 g / Equivalent) 210 g (epoxy group 1.0 mol), except for changing to hydroquinone 0.13 g and TPP (triphenylphosphine) 0.75 g, the same operation as in Example 1, and containing (meth) acryloyl group Resin (1 ′) was obtained. The obtained (meth) acryloyl group-containing resin (1 ′) had a solid content of 65% by mass, and the (meth) acryloyl group equivalent of solids calculated from the raw material charge ratio was 282 g / equivalent.

Examples 5 to 8 and Comparative Example 1
Various evaluations were performed by adjusting the curable resin material in the following manner. The results are shown in Table 1.

<Adjustment of curable resin material>
Each component was mix | blended in the ratio shown in Table 1, and it mixed with the rotation revolution type stirrer which attached the cooling device, and prepared curable resin material. Details of each component described in the table are as follows.
Polymerization initiator 1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one polymerization initiator 2: 2, 4-diethylthioxanthone DPHA: dipentaerythritol hexaacrylate pigment: phthalocyanine green Filler: Talc

<Evaluation of dryness>
The curable resin material prepared above was applied to a polyimide film substrate in a thickness of 60 μm and preliminarily dried at 80 ° C. for 30 minutes. After cooling the coating film to room temperature, the adhesion state when the solder mask pattern was superimposed on the coating film surface was observed to evaluate the drying property.
○: Solder mask pattern does not adhere to resin coating film ×: Solder mask pattern adheres to resin coating film

<Evaluation of sensitivity>
The curable resin material prepared above was applied to a polyimide film substrate in a thickness of 60 μm and preliminarily dried at 80 ° C. for 30 minutes. A 21-step tablet (manufactured by Kodak Co., Ltd.) was brought into close contact with the coating film and irradiated with ultraviolet rays using a metal halide lamp exposure device (manufactured by Oak Manufacturing). Next, a 1 wt% aqueous sodium carbonate solution at 30 ° C. was used for development processing at a spray pressure of 2.0 kg / cm ² for 60 seconds, followed by curing at 150 ° C. for 30 minutes to obtain a sample. The sensitivity of the curable resin material was evaluated based on the number of stages of the cured resin remaining in the exposed area. Higher numbers indicate higher sensitivity.

<Evaluation of developer time>
The curable resin material prepared above was applied to a polyimide film substrate in a thickness of 60 μm and preliminarily dried at 80 ° C. for 30 minutes. A solder mask pattern is brought into close contact with the coating film, and irradiated with 200 mJ / cm ² of ultraviolet rays using a metal halide lamp exposure apparatus (manufactured by Oak Manufacturing Co., Ltd.) at a measuring position with an ultraviolet integrated intensity meter (manufactured by Eyegraphic Co., Ltd.). Development was carried out at a spray pressure of 2.0 kg / cm ² using a 1 wt% sodium carbonate aqueous solution at 0 ° C. The development state of the unexposed part was visually determined with a magnifying glass every 15 seconds, and the time until development was completed after the curable resin material in the unexposed part was completely removed was evaluated as development time (seconds).

<Evaluation of thermal management width>
The curable resin material prepared above was applied to a polyimide film substrate at a thickness of 60 μm, and samples were prepared by changing the preliminary drying time at 80 ° C. from 10 minutes to 90 minutes at 10 minute intervals. The maximum pre-drying time (minutes) of the resin film that was completely removed when the development process was performed for 60 seconds at a spray pressure of 2.0 kg / cm ² using a 1 wt% sodium carbonate aqueous solution at 30 ° C. The thermal management width was evaluated.

<Evaluation of solder heat resistance>
The curable resin material prepared above was applied to a polyimide film substrate in a thickness of 60 μm and preliminarily dried at 80 ° C. for 30 minutes. Using a metal halide lamp exposure device (manufactured by Oak Manufacturing Co., Ltd.), after irradiating with 200 mJ / cm ² of ultraviolet light in a measuring device with an ultraviolet integrated intensity meter (manufactured by Eye Graphic Co., Ltd.), curing was performed at 150 ° C. for 30 minutes to obtain a sample. It was. According to the test method of JIS C 6481, the sample was immersed in a solder bath at 260 ° C. for 10 seconds, and this was repeated three times. Evaluation was based on the maximum number of immersions that did not change the appearance.

<Evaluation of surface hardness of cured product>
The curable resin material prepared above was applied to a polyimide film substrate in a thickness of 60 μm and preliminarily dried at 80 ° C. for 30 minutes. Using a metal halide lamp exposure device (manufactured by Oak Manufacturing Co., Ltd.), after irradiating with 200 mJ / cm ² of ultraviolet light in a measuring device with an ultraviolet integrated intensity meter (manufactured by Eye Graphic Co., Ltd.), curing was performed at 150 ° C. for 30 minutes to obtain a sample. It was. The pencil hardness of the coating film surface of the sample was tested according to the test method of JIS K 5400, and the highest hardness at which the coating film was not damaged was observed.

<Base material adhesion>
The previously prepared curable resin material was applied on a copper clad laminate at a thickness of 60 μm and pre-dried at 80 ° C. for 30 minutes. Using a metal halide lamp exposure device (Oak Seisakusho), the sample was irradiated with 200 mJ / cm ² of ultraviolet rays in a measuring device with an ultraviolet integrated intensity meter (made by Eye Graphic Co., Ltd.) and then cured at 150 ° C. for 30 minutes. Obtained. A 10 × 10 cross cut with a width of 1 mm was placed on the resin coating, a peel test was performed with a cellophane tape, and the peeled state was visually observed.
○: No peeling is observed Δ: 1-10 peeling is observed x: 10 or more peeling

<Acid resistance of cured product>
The curable resin material prepared above was applied to a polyimide film substrate in a thickness of 60 μm and preliminarily dried at 80 ° C. for 30 minutes. Using a metal halide lamp exposure device (manufactured by Oak Manufacturing Co., Ltd.), after irradiating with 200 mJ / cm ² of ultraviolet light in a measuring device with an ultraviolet integrated intensity meter (manufactured by Eye Graphic Co., Ltd.), curing was performed at 150 ° C. for 30 minutes to obtain a sample. It was. The state of the cured coating film after the sample was immersed in 10% by weight hydrochloric acid for 30 minutes was evaluated.
○: No change is observed at all ×: The cured coating is swollen and peeled off

<Solvent resistance of cured product>
The curable resin material prepared above was applied to a polyimide film substrate in a thickness of 60 μm and preliminarily dried at 80 ° C. for 30 minutes. Using a metal halide lamp exposure device (manufactured by Oak Manufacturing Co., Ltd.), after irradiating with 200 mJ / cm ² of ultraviolet light in a measuring device with an ultraviolet integrated intensity meter (manufactured by Eye Graphic Co., Ltd.), curing was performed at 150 ° C. for 30 minutes to obtain a sample. It was. The state of the cured coating film after the sample was immersed in methylene chloride for 30 minutes was evaluated.
○: No change is observed at all ×: The cured coating is swollen and peeled off

<PCT resistance of cured product>
The curable resin material prepared above was applied to a polyimide film substrate in a thickness of 60 μm and preliminarily dried at 80 ° C. for 30 minutes. Using a metal halide lamp exposure device (manufactured by Oak Manufacturing Co., Ltd.), after irradiating with 200 mJ / cm ² of ultraviolet light in a measuring device with an ultraviolet integrated intensity meter (manufactured by Eye Graphic Co., Ltd.), curing was performed at 150 ° C. for 30 minutes to obtain a sample. It was. The state of the cured coating film when the sample was exposed to saturated steam at 121 ° C. for 50 hours was evaluated.
○: No change was observed in the cured coating film before and after the test. ×: The cured coating film was swollen and peeled off.

<Electric reliability of cured product>
The curable resin material prepared above was applied to a polyimide film substrate in a thickness of 60 μm and preliminarily dried at 80 ° C. for 30 minutes. A solder mask pattern was brought into close contact with the coating film, and using a metal halide lamp exposure apparatus (manufactured by Oak Manufacturing Co., Ltd.), 200 mJ / cm ² of ultraviolet rays were irradiated with a measuring device using an ultraviolet integrated intensity meter (manufactured by Eyegraphic). Using a 1 wt% sodium carbonate aqueous solution at 30 ° C., development was performed at a spray pressure of 2.0 kg / cm 2 for 60 seconds, followed by curing at 150 ° C. for 30 minutes to obtain a sample. The electrical insulation properties of the samples were evaluated under the following conditions.
Humidification conditions: temperature 120 ° C., humidity 95% RH, applied voltage 30 V, 100 hours Measurement conditions: measurement time 60 seconds, applied voltage 500 V
○: Insulation resistance value after humidification of 10 ⁻¹⁰ Ω or more, no copper migration Δ: Insulation resistance value after humidification of 10 ⁻¹⁰ Ω or more, with copper migration ×: Insulation resistance value after humidification of 10 ⁻⁹ Ω or less, With copper migration

<Flame retardancy of cured product>
Using the curable resin material prepared above, flame retardancy was evaluated in accordance with ASTM D4804-03. Five samples were prepared, each sample was contacted twice for 3 seconds, the burning time was measured 10 times in total, and judged according to the following criteria.
VTM-0: individual combustion time 10 seconds or less and total combustion time 50 seconds or less VTM-1: individual combustion time 30 seconds or less and total combustion time 250 seconds or less VTM-2: individual combustion time 30 seconds or less, And the total combustion time is 250 seconds or less, and the burned material falls BURN: individual combustion time is 30 seconds or more, or total combustion time is 250 seconds or more

<Heat resistance of cured product>
On the mirror surface aluminum plate, the previously prepared curable resin material was applied in a thickness of 60 μm and pre-dried at 80 ° C. for 30 minutes. Using a metal halide lamp exposure apparatus (manufactured by Oak Manufacturing Co., Ltd.), after irradiating 200 mJ / cm ² of ultraviolet light in a measuring device with an ultraviolet integrated intensity meter (manufactured by Eye Graphic Co., Ltd.), curing was performed at 150 ° C. for 30 minutes to obtain a sample. It was. A sample was cut into a size of 5 mm in width and 54 mm in length, and this was used as a test piece as a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., Ltd., rectangular tension method: frequency 1 Hz, heating rate 3 ° C. / Min) was used to evaluate the glass transition temperature at the temperature at which the elastic modulus change was maximum (the tan δ change rate was the largest).

Claims (11)

The following structural formula (4)

[Wherein Y represents the following structural formula (1-1) or (1-2)

(In the formula, R ¹ represents a hydrogen atom or a methyl group.)
Wherein each R ⁴ independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or the following structural formula (5):

{Wherein Y is a structural moiety (Y) represented by the structural formula (1-1) or (1-2), and R ⁵ independently represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. , M is an integer of 1-6. }
Wherein m is an integer of 1 to 6, and n is an integer of 1 to 4. ]
(Meth) acryloyl group containing resin represented by these. The (meth) acryloyl group-containing resin according to claim 1, wherein the bonding position of the oxygen atom on the naphthalene skeleton in the structural formula (4) is in the 1,6-position or 2,7-position. The (meth) acryloyl group-containing resin according to claim 1 or 2, wherein the (meth) acryloyl group equivalent is in the range of 200 to 1000 g / equivalent. Dihydroxynaphthalene and an aralkylating agent are reacted under acid catalyst conditions to obtain a polynaphthylene ether intermediate (α), which is reacted with an epihalohydrin to obtain an epoxy resin intermediate (β). React with a (meth) acrylic acid derivative ,
The following structural formula (4)

[Wherein Y represents the following structural formula (1-1) or (1-2)

(In the formula, R ¹ represents a hydrogen atom or a methyl group.)
Wherein each R ⁴ independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or the following structural formula (5):

{Wherein Y is a structural moiety (Y) represented by the structural formula (1-1) or (1-2), and R ⁵ independently represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. , M is an integer of 1-6. }
Wherein m is an integer of 1 to 6, and n is an integer of 1 to 4. ]
(Meth) acryloyl group containing resin represented by these is obtained , The manufacturing method of (meth) acryloyl group containing resin characterized by the above-mentioned. The method for producing a (meth) acryloyl group-containing resin according to claim 4, wherein the aralkylating agent is benzyl chloride, benzyl bromide, or benzyl alcohol. Dihydroxynaphthalene is reacted under alkaline catalyst conditions to obtain a polynaphthylene ether intermediate (γ), and this is reacted with epihalohydrin to obtain an epoxy resin intermediate (ε), which is further (meth) acrylic acid derivative. is reacted with,
The following structural formula (4)

[Wherein Y represents the following structural formula (1-1) or (1-2)

(In the formula, R ¹ represents a hydrogen atom or a methyl group.)
Wherein each R ⁴ independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or the following structural formula (5):

{Wherein Y is a structural moiety (Y) represented by the structural formula (1-1) or (1-2), and R ⁵ independently represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. , M is an integer of 1-6. }
Wherein m is an integer of 1 to 6, and n is an integer of 1 to 4. ]
(Meth) acryloyl group containing resin represented by these is obtained , The manufacturing method of (meth) acryloyl group containing resin characterized by the above-mentioned. The method for producing a (meth) acryloyl group-containing resin according to any one of claims 4 to 6, wherein the dihydroxynaphthalene is 1,6-dihydroxynaphthalene or 2,7-dihydroxynaphthalene. A curable resin material containing the (meth) acryloyl group-containing resin according to any one of claims 1 to 3 as an essential component. A cured product obtained by curing the curable resin material according to claim 8. The resist material containing the (meth) acryloyl group containing resin as described in any one of Claims 1-3, and alkali developable resin. A resist pattern comprising the resist material according to claim 10.

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