WO2017204206A1 - Resin composition and resist film - Google Patents

Abstract

To provide a resin composition having excellent heat resistance and dry etching resistance that can be used suitably as a resin material for a resist, a cured product thereof, a resin material for a resist made using the resin composition, and a resist film. A resin composition characterized by containing an epoxy resin (A) having a polyarylene ether structure (α) and a hydroxynaphthalene novolac phenol resin (B), a cured product of said composition, a resin material for a resist obtained using the resin composition, and a resist film.

Description

Resin composition and resist film

The present invention relates to a resin composition excellent in heat resistance and dry etching resistance, and a resist film using the same.

In addition to being used for adhesives, molding materials, paints, photoresist materials, epoxy resin raw materials, epoxy resin curing agents, etc., phenolic hydroxyl group-containing resins are excellent in heat resistance and moisture resistance in cured products, As a curable composition containing a phenolic hydroxyl group-containing resin itself as a main ingredient, or as a curing agent such as an epoxy resin, it is widely used in the electrical and electronic fields such as semiconductor sealing materials and insulating materials for printed wiring boards.

Among these, in the field of photoresists, a variety of resist pattern forming methods that have been subdivided according to applications and functions have been developed one after another, and the performance requirements for resist resin materials have become sophisticated and diversified accordingly. . For example, not only high developability for forming a fine pattern accurately and with high production efficiency on a highly integrated semiconductor, but also when used as a resist underlayer film, dry etching resistance, heat resistance, etc. are required. Moreover, when using for a resist permanent film, especially high heat resistance is requested | required.

The phenolic hydroxyl group-containing resin most widely used for photoresist applications is of the cresol novolac type, but as mentioned above, it does not meet the demands of today's increasingly sophisticated and diversified markets, and is heat resistant. Also, developability was not sufficient (see Patent Document 1).

JP-A-2-55359

Therefore, a problem to be solved by the present invention is to provide a resin composition excellent in heat resistance and dry etching resistance and a resist film using the same.

As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition containing an epoxy resin (A) having a polyarylene ether structure (α) and a hydroxynaphthalene novolac-type phenol resin (B). The product has been found to have characteristics excellent in heat resistance and dry etching resistance, and the present invention has been completed.

That is, the present invention relates to a resin composition comprising an epoxy resin (A) having a polyarylene ether structure (α) and a hydroxynaphthalene novolac type phenol resin (B).

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

The present invention further relates to a resist resin material using the resin composition.

The present invention further relates to a resist film using the resin composition.

According to the present invention, it is possible to provide a resin composition excellent in heat resistance and dry etching resistance and a resist film using the same.

Hereinafter, the present invention will be described in detail.
The resin composition of the present invention contains an epoxy resin (A) having a polyarylene ether structure (α) and a hydroxynaphthalene novolac-type phenol resin (B).

Regarding the epoxy resin (A) having the polyarylene ether structure (α), the arylene group forming the polyarylene ether structure is, for example, a phenylene group, a naphthylene group, and one of various substituents on these aromatic nuclei. Or a plurality of structural sites. Among these, since it becomes a resin composition excellent in heat resistance and dry etching resistance, a structure in which at least one of the arylene groups in the epoxy resin (A) has one or more various substituents on the naphthylene group or its aromatic nucleus It is preferably a site, more preferably 80% or more of the arylene group in the epoxy resin (A) is a structural site having one or a plurality of various substituents on the naphthylene group or its aromatic nucleus. The arylene ether structure (α) is particularly preferably a polynaphthylene ether structure.

As a specific structural example of the epoxy resin (A), for example, the following structural formula (3)

[Wherein Ar ¹ and Ar ² represent an aromatic ring, i is 0 or an integer of 1 to 5, and at least one of Ar ¹ and Ar ² present in the molecule is a naphthalene ring. R ³ each independently represents an alkyl group, an aryl group, an aralkyl group, a structural site in which one or more of hydrogen atoms contained therein are substituted with a glycidyloxy group, an alkoxy group or a halogen atom, a glycidyloxy group, an alkoxy group, It is any of halogen atoms, j is 0 or an integer of 1 to 4, and k is 0 or an integer of 1 to 5. ]
And a molecule having at least one glycidyloxy group in the molecule.

R ³ in the structural formula (3) is an alkyl group, an aryl group, an aralkyl group, a structural site in which one or more of hydrogen atoms contained therein are substituted with a glycidyloxy group, an alkoxy group or a halogen atom, glycidyloxy A group, an alkoxy group, or a halogen atom.
Examples of the alkyl group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. Examples of the aryl group include aryl groups such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Examples of the aralkyl group include a benzyl group, a diphenylmethyl group, a phenylethyl group, a naphthylmethyl group, and a naphthylethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, and a butyloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Among them, since R ³ is a resin composition excellent in heat resistance and dry etching resistance, R ³ is glycidyloxy group, glycidyloxyphenyl group, glycidyloxynaphthyl group, benzyl group, phenylethyl group, naphthylmethyl group, naphthylethyl group. It is preferable that it is either. Moreover, it is preferable that two Ar < ¹ > in the said Structural formula (3) has a glycidyloxy group, respectively.

When the polyarylene ether structure (α) is a polynaphthylene ether structure, a more preferable specific structural example of the epoxy resin (A) is, for example, the following structural formula (4)

[Wherein i is 0 or an integer of 1 to 5. R ⁴ each independently represents an alkyl group, an aryl group, an aralkyl group, a structural site in which one or more of hydrogen atoms contained therein are substituted with a glycidyloxy group, an alkoxy group or a halogen atom, an alkoxy group, or a halogen atom. P is 0 or an integer from 1 to 4, and q is 0 or an integer from 1 to 4. ]
The thing which has the molecular structure represented by these is mentioned.

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. Of these, the 1,6-position or 2,7-position is preferred, and the 2,7-position is particularly preferred, because the resin composition is excellent in heat resistance and dry etching resistance.

I in the structural formula (3) and the structural formula (4) is 0 or an integer of 1 to 4. Especially, since it becomes a resin composition excellent in heat resistance and dry etching resistance, it is preferable that the epoxy resin (A) contains the component whose i is 0 or 1.

Further, the sum of the aromatic nuclei represented by Ar ¹ , Ar ² and R ³ in the structural formula (3), or the sum of the naphthalene ring and the aromatic nuclei represented by R ⁴ in the structural formula (4). Is preferably in the range of 4 to 12 because it provides a resin composition having excellent heat resistance and dry etching resistance.

The epoxy group content of the epoxy resin (A) is preferably in the range of 200 to 350 g / equivalent because it becomes a resin composition excellent in heat resistance and dry etching resistance.

The softening point of the epoxy resin (A) is preferably in the range of 80 to 140 ° C. because of its excellent solubility in organic solvents.

The epoxy resin (A) is, for example, a method in which an aromatic dihydroxy compound (a1) is reacted under an acid or alkali catalyst condition to obtain a polyarylene ether resin intermediate, and this is reacted with an epihalohydrin to form an epoxy resin. Can be manufactured. Specific examples of such a production method include the following two methods.
Method 1: A method in which an aromatic dihydroxy compound (a1) and an aralkylating agent (a2) are reacted under acid catalyst conditions to obtain a polyarylene ether resin intermediate (1), which is then reacted with an epihalohydrin.
Method 2: A method in which an aromatic dihydroxy compound (a1) is reacted under alkaline catalyst conditions to obtain a polyarylene ether resin intermediate (2), which is reacted with an epihalohydrin.

The method 1 will be described. The aromatic dihydroxy compound (a1) used in Method 1 is, for example, dihydroxybenzene such as 1,2-benzenediol, 1,3-benzenediol, 1,4-benzenediol; 1,2-dihydroxynaphthalene, 1, Dihydroxynaphthalene such as 4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene Etc. These may be used alone or in combination of two or more. Among them, dihydroxynaphthalene is preferable because it is a resin composition excellent in heat resistance and dry etching resistance, 1,6-dihydroxynaphthalene or 2,7-dihydroxynaphthalene is more preferable, and 2,7-dihydroxynaphthalene is particularly preferable.

The aralkylating agent (a2) used in Method 1 is, for example, the following structural formulas (5-1) to (5-3)

[Wherein X represents a halogen atom. R ⁵ is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; Ar ³ is a phenyl group, a naphthyl group, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group on the aromatic nucleus thereof Any one of a plurality of structural sites. ]
The compound represented by either of these is mentioned. These aralkylating agents (a2) may be used alone or in combination of two or more.

Among the compounds represented by any one of the structural formulas (5-1) to (5-3), the compound represented by the structural formula (5-1) is preferable because of its high reactivity. A compound in which Ar ³ is a phenyl group or a naphthyl group is more preferable.

The reaction ratio between the aromatic dihydroxy compound (a1) and the aralkylating agent (a2) is such that the molar ratio [(a1) / (a2)] is 1.0 / 0.1 to 1.0 / 1.0. It is preferable that the ratio is

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. When an inorganic acid or an organic acid is used as the acid catalyst, it is preferably used in the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the aromatic dihydroxy compound (a1). When a Friedel-Crafts catalyst is used as the acid catalyst, it is preferably used in a range of 0.2 to 3.0 moles with respect to 1 mole of the aromatic dihydroxy compound (a1).

The reaction of the aromatic dihydroxy compound (a1) and the aralkylating agent (a2) 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 kinds of mixed solvents may be used.

The reaction between the aromatic dihydroxy compound (a1) and the aralkylating agent (a2) can be performed under a temperature condition of about 100 to 180 ° C. After the reaction is completed, an alkali compound such as an alkali metal hydroxide is added. After neutralizing the inside of the reaction system, the water and organic solvent produced in the reaction can be dried under reduced pressure to obtain the polyarylene ether resin intermediate (1).

The polyarylene ether resin intermediate (1) obtained in the first step of Method 1 preferably has a hydroxyl equivalent in the range of 150 to 200 g / equivalent.

Then, in the second step of Method 1, the obtained polyarylene ether resin intermediate (1) is reacted with epihalohydrin. The reaction uses, for example, 2 to 10 moles of epihalohydrin with respect to 1 mole of hydroxyl groups of the polyarylene ether resin intermediate (1), and 1 mole of hydroxyl groups of the polyarylene ether resin intermediate (1). A method of reacting at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while adding 0.9 to 2.0 mol of a basic catalyst all at once or in a divided manner.

Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. These may be used alone or in combination of two or more. Among these, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity, and specifically sodium hydroxide and potassium hydroxide are preferable.

Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. These may be used alone or in combination of two or more. Of these, epichlorohydrin is preferred because it is easily available industrially. In addition, surplus epihalohydrin used in the reaction can be recovered, and this recovered epihalohydrin may be reused when the epoxy resin (A) is industrially produced.

The reaction between the polyarylene ether resin intermediate (1) and epihalohydrin may be performed in an organic solvent. Examples of the organic solvent used here include ketonic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbon solvents such as toluene and xylene, methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, and 1-butanol. Alcoholic solvents such as secondary butanol and tertiary butanol, cellosolve solvents such as methyl cellosolve and ethyl cellosolve, ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, acetonitrile, dimethyl sulfoxide, Examples include aprotic polar solvents such as dimethylformamide. These organic solvents may be used alone or in combination of two or more.

After completion of the reaction, the reaction mixture is washed with water, and unreacted epihalohydrin and the organic solvent are distilled off by distillation under heating and reduced pressure. In addition, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is dissolved again in an organic solvent, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added for further reaction. Can also be done. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the epoxy resin. After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the organic solvent is distilled off under heating and reduced pressure to obtain the desired epoxy resin (A).

The epoxy resin (A) obtained by the above method 1 is, for example, when 2,7-dihydroxynaphthalene is used as the aromatic dihydroxy compound (a1) and benzyl alcohol is used as the aralkylating agent. And those represented by any one of (6-1) to (6-18). In the formula, G represents a glycidyl group, and Bn represents a benzyl group.

Next, the method 2 will be described. The aromatic dihydroxy compound (a1) used in Method 2 is the same as that described in the description of Method 1.

Examples of the alkali catalyst used in Method 2 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 moles per mole of the aromatic dihydroxy compound (a1).

The polycondensation reaction of the aromatic dihydroxy compound (a1) 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. These may be used alone or in combination of two or more.

The polycondensation reaction of the aromatic dihydroxy compound (a1) can be performed, for example, under a temperature condition 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 removed from the organic layer. The polyarylene ether resin intermediate (2) can be obtained by drying under reduced pressure.

The polyarylene ether resin intermediate (2) obtained in the first step of Method 2 preferably has a hydroxyl equivalent in the range of 100 to 150 g / equivalent.

The second step of Method 2 can be performed by the same method as the second step of Method 1.

For example, when 2,7-dihydroxynaphthalene is used as the aromatic dihydroxy compound (a1), the epoxy resin (A) obtained by the method 2 specifically has the following structural formulas (7-1) to (7 -11) or the like. In the formula, G represents a glycidyl group.

The hydroxy naphthalene novolak type phenol resin (B) used in the present invention is specifically a polycondensation reaction product containing a hydroxy naphthalene compound (b1) and an aldehyde compound (b2) as essential reaction components.

Examples of the hydroxy naphthalene compound (b1) include naphthol, dihydroxynaphthalene, and compounds having one or more substituents such as a halogen atom, an alkyl group, and an alkoxy group on the aromatic nucleus. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the alkyl group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, and a butyloxy group. These hydroxy naphthalene compounds (b1) may be used alone or in combination of two or more. Among them, naphthol or dihydroxynaphthalene is preferable because it is a resin composition excellent in heat resistance and dry etching resistance.

The hydroxy naphthalene novolak-type phenol resin (B) of the present invention may be a combination of other phenolic hydroxyl group-containing compound (b3) other than the hydroxy naphthalene compound (b1). Examples of the other phenolic hydroxyl group-containing compound (b3) include phenol, dihydroxybenzene, anthracenol, a compound having one or more substituents such as a halogen atom, an alkyl group, and an alkoxy group on the aromatic nucleus. Is mentioned. These may be used alone or in combination of two or more. When these other phenolic hydroxyl group-containing compounds (b3) are used, the resulting resin composition is excellent in heat resistance and dry etching resistance. Therefore, the hydroxynaphthalene compound (b1) and the other phenolic hydroxyl group-containing compounds ( The ratio of the hydroxy naphthalene compound (b1) to the sum of b3) is preferably 50 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

Examples of the aldehyde compound (b2) include formaldehyde, alkyl aldehydes such as acetaldehyde, propyl aldehyde, and butyraldehyde, and aromatic aldehydes such as benzaldehyde, naphthaldehyde, hydroxybenzaldehyde, and hydroxynaphthaldehyde. These may be used alone or in combination of two or more.

The hydroxy naphthalene novolac type phenol resin (B) has the following structural formula (1)

(In the formula, l is 1 or 2, and the hydroxyl group may be bonded to any carbon atom on the naphthalene ring. R ¹ represents a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Each of R ² is independently an alkyl group, an alkoxy group, or a halogen atom, and may be bonded to any carbon atom on the naphthalene ring; m is 0 or an integer of 1 to 5.)
A chain-like acyclic novolac resin (B1) having a structural site (β) represented by the following structural unit may be used, or the following structural formula (2)

[Wherein β is the structural moiety (β) represented by the structural formula (1), and n is an integer of 2 to 10. ]
A cyclic novolac resin (B2) having a molecular structure represented by Further, it may be a mixture of the non-cyclic novolac resin (B1) and the cyclic novolac resin (B2).

The hydroxy naphthalene novolac type phenol resin (B) preferably contains the cyclic novolac type resin (B2) from the viewpoint of further improving heat resistance and dry etching resistance. In particular, the ratio of the cyclic novolac resin (B2) in the hydroxy naphthalene novolac phenol resin (B) is preferably 3% or more, more preferably 30% or more, and 75% or more. Is particularly preferred.

The hydroxy naphthalene novolac type phenolic resin (B) is a resin composition having excellent heat resistance and dry etching resistance, so that the weight average molecular weight (Mw) is preferably in the range of 300 to 30,000, and polydispersed. The degree (Mw / Mn) is preferably in the range of 1.1 to 5.

In the present invention, the weight average molecular weight (Mw) and polydispersity (Mw / Mn) are values measured by GPC under the following conditions. Moreover, the ratio of the said cyclic novolak-type resin (B2) in the said hydroxy naphthalene novolak-type phenol resin (B) is a value calculated from the area ratio of the GPC chart figure measured on condition of the following.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK + “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK
+ Showa Denko Co., Ltd. “Shodex KF803” (8.0 mmФ × 300 mm) + Showa Denko Co., Ltd. “Shodex KF804” (8.0 mmФ × 300 mm)
Column temperature: 40 ° C
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.30” manufactured by Tosoh Corporation
Developing solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample: Filtered 0.5% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)
Standard sample: Monodispersed polystyrene below (Standard sample: Monodispersed polystyrene)
“A-500” 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

The hydroxy naphthalene novolac type phenolic resin (B) is a resin composition having excellent heat resistance and dry etching resistance, so that the residual monomer amount is preferably 1% by mass or less.

The production method of the hydroxy naphthalene novolac type phenol resin (B) is not particularly limited. For example, the hydroxy naphthalene compound (b1), the aldehyde compound (b2), and the other phenolic hydroxyl group-containing compound (if necessary) ( A method of reacting b3) in the presence of an acid catalyst or an alkali catalyst in a temperature range of about 60 to 200 ° C. for 0.5 to 100 hours can be mentioned.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Is mentioned. These may be used alone or in combination of two or more. The amount of these acid catalysts used is preferably in the range of 0.1 to 5% by mass relative to the total mass of the reaction raw materials.

Examples of the alkali catalyst 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.

For the acid catalyst and the alkali catalyst, it is usually preferable to use an acid catalyst as in the case of producing a general phenol novolac resin. The alkali catalyst is used, for example, in the case of producing hydroxynaphthalene novolac type phenol resin (B) containing the cyclic novolac type resin (B2) using formaldehyde as the aldehyde compound (b2).

The reaction may be performed in an organic solvent as necessary. Examples of the solvent used here include monoalcohols such as methanol, ethanol, and propanol; monocarboxylic acids such as acetic acid, propionic acid, butyric acid, pentanoic acid, and hexanoic acid; ethylene glycol, 1,2-propanediol, 1,3- Propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol Polyols such as polyethylene glycol and glycerin; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol Glycol ethers such as monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether and ethylene glycol monophenyl ether; cyclic ethers such as 1,3-dioxane, 1,4-dioxane and tetrahydrofuran; glycol esters such as ethylene glycol acetate; Examples include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. These solvents may be used alone or in combination of two or more kinds.

In the case of producing a hydroxy naphthalene novolak type phenolic resin (B) having the acyclic novolac type resin (B1) as a main component, a ketone compound is preferably used as a reaction solvent. On the other hand, when producing the hydroxy naphthalene novolac type phenol resin (B) containing the cyclic novolac type resin (B2), it is preferable to use an alcohol solvent.

After completion of the reaction, the reaction mixture is neutralized or washed with water, and then the unreacted reaction raw materials and by-products are distilled off to obtain the hydroxy naphthalene novolak type phenol resin (B).

The resin composition of the present invention described in detail above can be used for various electric and electronic member applications such as adhesives, paints, photoresists, printed wiring boards and the like, taking advantage of its excellent heat resistance. Among these applications, it is particularly suitable for resist applications that take advantage of heat resistance and excellent dry etching resistance, and can be suitably used for thick film resist applications, resist underlayer films, and resist permanent film applications. It can also be used as a heat resistance imparting agent for photosensitive resist materials.

The curable composition of the present invention may contain other compounds in addition to the epoxy resin (A) and the hydroxy naphthalene novolac type phenol resin (B). Other compounds include, for example, other epoxy resins (A ′) other than the epoxy resin (A), other phenol resins (B ′) other than the hydroxy naphthalene novolac type phenol resin (B), and various vinyl polymers. , Melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, resol resins, isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, acid anhydrides, oxazoline compounds, imidazole compounds, phosphorus compounds, amines Compounds and the like.

Examples of the other epoxy resin (A ′) include diglycidyloxynaphthalene, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, and naphthol-cresol co-polymer. Condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane, naphthylene ether type epoxy resin, triphenylmethane type epoxy resin Resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phosphorus atom-containing epoxy resin, co-condensation product of phenolic hydroxyl group-containing compound and alkoxy group-containing aromatic compound Le, and the like.

The other phenol resin (B ′) is, for example, a novolak resin using one or more phenol raw materials such as phenol, cresol, xylenol, phenylphenol, resorcinol, biphenyl, bisphenol, and alicyclic such as dicyclopentadiene. Addition polymerization resin of diene compound and phenol compound, modified novolak resin of phenolic hydroxyl group-containing compound and alkoxy group-containing aromatic compound, phenol aralkyl resin (Zyrock resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane Examples thereof include resins and aminotriazine-modified phenolic resins.

The various vinyl polymers include polyhydroxystyrene, polystyrene, polyvinyl naphthalene, polyvinyl anthracene, polyvinyl carbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, poly ( A homopolymer of a vinyl compound such as (meth) acrylate or a copolymer thereof may be mentioned.

Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol melamine methylol Examples include compounds in which 1 to 6 groups are acyloxymethylated. *

Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, tetramethoxymethyl benzoguanamine, a compound in which 1 to 4 methylol groups of tetramethylol guanamine are methoxymethylated, tetramethoxyethyl guanamine, tetraacyloxyguanamine, tetra Examples thereof include compounds in which 1 to 4 methylol groups of methylolguanamine are acyloxymethylated.

Examples of the glycoluril compound include 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4,6-tetrakis ( Hydroxymethyl) glycoluril and the like.

Examples of the urea compound include 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea and 1,1,3,3-tetrakis (methoxymethyl) urea. It is done.

The resole resin may be, for example, an alkylphenol such as phenol, cresol or xylenol, a bisphenol such as phenylphenol, resorcinol, biphenyl, bisphenol A or bisphenol F, a phenolic hydroxyl group-containing compound such as naphthol or dihydroxynaphthalene, and an aldehyde compound. Examples include polymers obtained by reacting under catalytic conditions.

Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.

Examples of the azide compound include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidenebisazide, 4,4'-oxybisazide, and the like.

Examples of the compound containing a double bond such as an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether. , Neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether Etc.

Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4,4 Aromatic acid anhydrides such as '-(isopropylidene) diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride And alicyclic carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, and trialkyltetrahydrophthalic anhydride.

Examples of the imidazole compound include 2-ethyl-4-methylimidazole. Examples of the phosphorus compound include triphenylphosphine. Examples of the amine compound include 1,8-diazabicyclo- [5.4.0] -undecene.

In the resin composition of the present invention, the blending ratio of each component can be appropriately adjusted according to desired performance and the like, and is not particularly limited. When the resin composition of the present invention is used for paints, semiconductor encapsulants, printed wiring board applications, etc., the number of moles of all epoxy groups in the resin composition relative to 1 mole of all phenolic hydroxyl groups in the resin composition. Is preferably blended at a ratio of 0.8 to 1.2. On the other hand, when the resin composition of the present invention is used for a resist film, the number of moles of all epoxy groups in the resin composition is 0.01 to 0.003 per mole of all phenolic hydroxyl groups in the resin composition. The range is preferably 8 mol, more preferably 0.01 to 0.6 mol, and particularly preferably 0.01 to 0.5 mol.

When the resin composition of the present invention is used for resist underlayer film (BARC film), various additives such as surfactants, dyes, fillers, cross-linking agents, and dissolution accelerators are added as necessary. It can be set as the composition for resist underlayer films by melt | dissolving in a solvent.

The organic solvent used in the resist underlayer film composition is not particularly limited. For example, alkylene glycol monoalkyl such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether propylene glycol monomethyl ether, etc. Ethers; Dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; alkylene groups such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate Cole alkyl ether acetate; Ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; Cyclic ethers such as dioxane; Methyl 2-hydroxypropionate, Ethyl 2-hydroxypropionate, Ethyl 2-hydroxy-2-methylpropionate , Ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, acetoacetic acid Examples thereof include ester compounds such as ethyl, and these may be used alone or in combination of two or more.

The resist underlayer film composition can be produced by blending the above components and mixing them using a stirrer or the like. When the resist underlayer film composition contains a filler or a pigment, it can be produced by dispersing or mixing using a dispersing device such as a dissolver, a homogenizer, or a three roll mill.

In order to prepare a resist underlayer film from the resist underlayer film composition, for example, the resist underlayer film composition is applied onto an object to be subjected to photolithography such as a silicon substrate, and is subjected to a temperature condition of 100 to 200 ° C. After drying, a resist underlayer film is formed by a method such as heat curing under a temperature condition of 250 to 400 ° C. Next, a resist pattern is formed on this lower layer film by performing a normal photolithography operation, and a resist pattern by a multilayer resist method can be formed by performing a dry etching process with a halogen-based plasma gas or the like.

When the resin composition of the present invention is used for resist permanent film applications, various additives such as surfactants, dyes, fillers, crosslinking agents, and dissolution accelerators are further added as necessary to dissolve in organic solvents. Thus, a composition for a resist permanent film can be obtained. The organic solvent used here is the same as the organic solvent used in the resist underlayer film composition.

A photolithography method using the resist permanent film composition includes, for example, dissolving and dispersing a resin component and an additive component in an organic solvent, and applying the solution on an object to be subjected to silicon substrate photolithography, and a temperature of 60 to 150 ° C. Pre-bake under the following temperature conditions. The coating method at this time may be any method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor blade coating and the like. Next, when creating the resist pattern, if the resist permanent film composition is positive, the target resist pattern is exposed through a predetermined mask, and the exposed portion is dissolved with an alkali developer. Thus, a resist pattern is formed.

The permanent film made of the resist permanent film composition is, for example, a solder resist, a package material, an underfill material, a package adhesive layer such as a circuit element, an integrated circuit element-circuit board adhesive layer, an LCD, or an OELD for semiconductor devices. Can be suitably used for thin film transistor protective films, liquid crystal color filter protective films, black matrices, spacers and the like.

When the resin composition of the present invention is used as a heat resistance imparting agent for a photosensitive resist material, it is preferably used in a range of 0.05 to 20 parts by mass in 100 parts by mass of the photosensitive resist material. Any known and commonly used photosensitive resist material can be used.

Specific examples of resins for photosensitive resist materials include various phenol resins, hydroxy groups such as p-hydroxystyrene and p- (1,1,1,3,3,3-hexafluoro-2-hydroxypropyl) styrene. -Containing styrene polymer, a hydroxyl group of the phenol resin or hydroxy group-containing styrene polymer modified with an acid-decomposable group such as t-butoxycarbonyl group or benzyloxycarbonyl group, a homopolymer or copolymer of (meth) acrylic acid Examples thereof include an alternating polymer of a polymer, an alicyclic polymerizable monomer such as a norbornene compound or a tetracyclododecene compound, and maleic anhydride or maleimide.

Photosensitive agents for photosensitive resist materials include, for example, aromatic (poly) hydroxy compounds, naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, orthoanthraquinonediazide Examples thereof include complete ester compounds, partial ester compounds, amidated products or partially amidated products with sulfonic acids having a quinonediazide group such as sulfonic acid. Examples thereof include compounds having a quinonediazide group such as a compound having a quinonediazide group.

Hereinafter, the present invention will be described in more detail with specific examples. In addition, the analysis of resin manufactured in the manufacture example was performed on the following conditions, respectively.

Number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity (Mw / Mn) were measured by GPC under the following conditions. The content of each component in the resin was calculated from the area ratio of the GPC chart measured under the following conditions.
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK + “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK
+ Showa Denko Co., Ltd. “Shodex KF803” (8.0 mmФ × 300 mm) + Showa Denko Co., Ltd. “Shodex KF804” (8.0 mmФ × 300 mm)
Column temperature: 40 ° C
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.30” manufactured by Tosoh Corporation
Developing solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample: 0.5% by mass tetrahydrofuran solution filtered with a microfilter in terms of resin solids Injection volume: 0.1 mL
Standard sample: Monodispersed polystyrene below (Standard sample: Monodispersed polystyrene)
“A-500” 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

[Measurement equipment for FD-MS]
Double convergence mass spectrometer AX505H (FD505H) manufactured by JEOL Ltd.

Production Example 1 Production of Epoxy Resin (A-1) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 160 parts by mass of 2,7-dihydroxynaphthalene, 25 parts by mass of benzyl alcohol, 160 parts by mass of xylene and 2 parts by mass of para-toluenesulfonic acid monohydrate were charged and stirred at room temperature while blowing nitrogen. The temperature was raised to 140 ° C., the generated water was distilled out of the system, and xylene distilled with water was stirred for 4 hours while returning to the reaction system. Next, the temperature was 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, the reaction mixture was neutralized by adding 2 parts by mass of a 20% aqueous sodium hydroxide solution and then dried under reduced pressure to obtain 178 parts by mass of a polyarylene ether resin intermediate (1-1). The intermediate (1-1) had a hydroxyl group equivalent of 169 g / equivalent and a softening point of 130 ° C.

The FD-MS of the polyarylene ether resin intermediate (1-1) and the FD-MS of the triarylated product of the polyarylene ether resin intermediate (1-1) were measured to confirm the formation of the following compounds.
1.2,7-dihydroxynaphthalene with one benzyl group added (M ⁺ = 250)
2. Two benzyl groups added to 2,7-dihydroxynaphthalene (M ⁺ = 340)
3. A compound in which n is 1 in the following structural formula (a) (M ⁺ = 446)
4). A compound in which n is 2 in the following structural formula (a) (M ⁺ = 588)
5). A compound in which one trimethylsilyloxynaphthyl group is added to a compound in which n is 1 in the following structural formula (a) (M ⁺ = 660)
6). A compound wherein n is 3 in the following structural formula (a) (M ⁺ = 730)
7). A compound in which one trimethylsilyloxynaphthyl group is added to a compound in which n is 2 in the following structural formula (a) (M ⁺ = 802)
8). A compound wherein n is 4 in the following structural formula (a) (M ⁺ = 873)
9. A compound in which one trimethylsilyloxynaphthyl group is added to a compound in which n is 3 in the following structural formula (a) (M ⁺ = 944)
10. A compound in which two trimethylsilyloxynaphthyl groups are added to a compound in which n is 2 in the following structural formula (a) (M ⁺ = 1016)
11. A compound in which one or two benzyl groups are added to each of the above 3 to 10 compounds

(In the formula, n is 0 or an integer of 1 or more, and TMS is a trimethylsilyl group.)

Into a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, 169 parts by mass of the polyarylene ether resin intermediate (1-1) obtained above while performing nitrogen gas purge, 463 parts by mass of epichlorohydrin, n-butanol 139 Part by mass and 2 parts by mass of tetraethylbenzylammonium chloride were charged and dissolved. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 90 parts by mass 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 by a Dean-Stark trap, the aqueous layer was removed, and the organic layer was returned to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. To the obtained crude epoxy resin, 432 parts by mass of methyl isobutyl ketone and 130 parts by mass of n-butanol were added and dissolved. Further, 10 parts by mass of a 10% aqueous sodium hydroxide solution was added and reacted at 80 ° C. for 2 hours. Subsequently, it washed with 150 mass parts of water until the pH of washing water became neutral. The system was dehydrated by azeotropic distillation, passed through microfiltration, and dried under reduced pressure to obtain 230 parts by mass of epoxy resin (A-1). The softening point of the epoxy resin (A-1) was 100 ° C., and the epoxy equivalent was 277 g / equivalent.

Production Example 2 Production of hydroxynaphthalene novolak type phenolic resin (B-1) In a 1 L four-necked flask equipped with a thermometer, a condenser tube and a stirrer, 144 parts by mass of 1-naphthol, 400 parts by mass of methyl isobutyl ketone, water 96 parts by mass and 27.7 parts by mass of 92% paraformaldehyde were charged. While stirring the inside of the flask, 4.8 parts by mass of an aqueous solution of paratoluenesulfonic acid adjusted to 50% by mass was added. The amount of water in the reaction system was 69.9 parts by mass with respect to 100 parts by mass of 1-naphthol. While stirring in the flask, the temperature was raised to 80 ° C. and reacted for 2 hours. During the reaction, the organic layer and the aqueous layer were not completely “uniform”, but were in a “non-uniform” state. After completion of the reaction, the organic layer was recovered using a separatory funnel. The organic layer was washed until the washing water showed neutrality, and then dried under heating and reduced pressure conditions to obtain 147 g of hydroxynaphthalene novolac type phenol resin (B-1). The number average molecular weight (Mn) of the hydroxy naphthalene novolak type phenol resin (B-1) is 1,312, the weight average molecular weight (Mw) is 2,251, the polydispersity (Mw / Mn) is 1.716, and the residual monomer amount Was 0.57 mass%.

Production Example 3 Production of Hydroxynaphthalene Novolak Type Phenolic Resin (B-2) A flask equipped with a thermometer, dropping funnel, condenser, and stirrer was charged with 288 parts by mass of 1-naphthol, 244 parts by mass of 4-hydroxybenzaldehyde, 1- 500 parts by weight of butanol and 14.4 parts by weight of 95% sulfuric acid were charged, heated to 80 ° C. and stirred for 17 hours. After completion of the reaction, 300 parts by mass of ethyl acetate and 160 parts by mass of ion exchange water were added, and the organic layer was recovered using a separatory funnel. The organic layer was washed with 160 parts by mass of ion-exchanged water, and washing with water was repeated until the pH of the washing water reached 4. After washing with water and drying with an evaporator, 466 parts by mass of a hydroxynaphthalene novolac type phenol resin (B-2) was obtained. From the GPC chart, it was confirmed that the hydroxynaphthalene novolac type phenol resin (B-2) contained 52% of a component represented by the following structural formula (2-1) and having n of 4. .

Production Example 4 Production of hydroxynaphthalene novolak type phenolic resin (B-3) A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was 216 parts by mass of 1-naphthol and 146 parts by mass of 37% formaldehyde aqueous solution. Parts, 121 parts by mass of isopropyl alcohol, and 46 parts by mass of a 49% aqueous sodium hydroxide solution were stirred at room temperature while blowing nitrogen. Subsequently, it heated up to 80 degreeC and made it react for 1 hour. After completion of the reaction, 40 parts by mass of first sodium phosphate was added for neutralization, and then the reaction solution was cooled to take out a crystal. The crystal was washed three times with 200 parts by mass of water and then dried under heating and reduced pressure to obtain 224 parts by mass of a hydroxynaphthalene novolac type phenol resin (B-3). From the GPC chart, it was confirmed that the hydroxynaphthalene novolak type phenol resin (B-3) contained 86% of a compound represented by the following structural formula (2-2) and n = 4. .

Production Example 5 Production of hydroxynaphthalene novolac-type phenolic resin (B-4) Same as Production Example 4 except that 1-naphthol (108 parts by mass) and 2-naphthol (108 parts by mass) were used instead of 1-naphthol (216 parts by mass) In this way, a hydroxy naphthalene novolak type phenol resin (B-4) was obtained. From the GPC chart, it is found that the hydroxy naphthalene novolak type phenolic resin (B-4) contains 6.9% of a compound represented by the following structural formula (2-3) where n is 4. confirmed.

Production Example 6 Production of Hydroxynaphthalene Novolak Type Phenolic Resin (B-5) Into a 1 L four-necked flask equipped with a thermometer, a condenser tube, a fractionating tube and a stirrer, 160 parts by mass of 2,7-dihydroxynaphthalene, methyl 400 parts by mass of isobutyl ketone, 96 parts by mass of water, and 27.7 parts by mass of 92% paraformaldehyde were charged. While stirring the inside of the flask, 4.8 parts by mass of an aqueous solution of paratoluenesulfonic acid adjusted to 50% concentration was added. The amount of water in the reaction system was 62.9 parts by mass with respect to 100 parts by mass of 2,7-dihydroxynaphthalene. While stirring in the flask, the temperature was raised to 80 ° C. and reacted for 2 hours. After completion of the reaction, the organic layer was recovered using a separatory funnel. The organic layer was washed with water until the washing water became neutral, and then dried under heating and reduced pressure conditions to obtain 165 parts by mass of a hydroxynaphthalene novolac type phenol resin (B-5). The number average molecular weight (Mn) of the hydroxy naphthalene novolak type phenol resin (B-5) is 1,142, the weight average molecular weight (Mw) is 1,626, and the polydispersity (Mw / Mn) is 1.424. The remaining amount was 0.61% by mass.

Production Example 7 Production of hydroxynaphthalene novolak-type phenolic resin (B-6) A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was charged with 48 parts by mass of 1,6-dihydroxynaphthalene, 26 masses of a 42 mass% formaldehyde aqueous solution. Part, 50 parts by mass of isopropyl alcohol, and 12.8 parts by mass of 48% potassium hydroxide were added and stirred at room temperature while blowing nitrogen. Then, it heated up at 80 degreeC and stirred for 1 hour. After completion of the reaction, 8 parts by mass of first sodium phosphate was added for neutralization, and the mixture was cooled and the crystals were separated by filtration. The crystallized product separated by filtration was washed three times with 50 parts by mass of water and then dried under heating and reduced pressure conditions to obtain 20 parts by mass of a hydroxynaphthalene novolac type phenol resin (B-6). From the GPC chart, it was confirmed that the hydroxy naphthalene novolak type phenol resin (B-6) contained 36% of a compound represented by the following structural formula (2-4) and having n of 4. .

Production Example 8 Production of hydroxynaphthalene novolac type phenolic resin (B-7) In a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, 160 parts by mass of 1,6-dihydroxynaphthalene and 122 parts by mass of 4-hydroxybenzaldehyde Then, 290 parts by mass of 2-ethoxyethanol and 1.7 parts by mass of 95% sulfuric acid were added, and the mixture was heated to 80 ° C. and stirred for 8 hours. After completion of the reaction, 300 parts by mass of ethyl acetate and 160 parts by mass of ion-exchanged water were added, and then the organic layer was recovered using a separatory funnel. The organic layer was washed with 160 parts by mass of ion-exchanged water until the pH of the washing water reached 4, and dried using an evaporator to obtain 247 parts by mass of a hydroxynaphthalene novolac type phenol resin (B-7). From the GPC chart, it was confirmed that the hydroxynaphthalene novolac-type phenol resin (B-7) contained 89% of a compound represented by the following structural formula (2-5), where n is 4. .

Production Example 9 Production of Hydroxynaphthalene Novolak Type Phenolic Resin (B-8) To a flask equipped with a thermometer, dropping funnel, condenser and stirrer, 80 parts by mass of 1,6-dihydroxynaphthalene, 72 parts by mass of 1-naphthol, 122 parts by weight of 4-hydroxybenzaldehyde, 290 parts by weight of 1-butanol, and 1.7 parts by weight of 95% sulfuric acid were charged, and the temperature was raised to 100 ° C. and the reaction was conducted for 12 hours with stirring. After completion of the reaction, 160 parts by mass of ion exchange water was added, and the organic layer was recovered using a separatory funnel. The organic layer was washed with 160 parts by weight of ion exchanged water until the pH of the washing water reached 4, and dried using an evaporator to obtain 237 parts by weight of a hydroxynaphthalene novolac type phenolic resin (B-8). From the GPC chart, it was confirmed that the hydroxynaphthalene novolac type phenolic resin (B-8) contained 79% of a cyclic novolac type resin represented by the following structural formula (2-6).

(Wherein l is 1 or 2, n is an integer of 2 to 10)

Examples 1-8
In the combination shown in Table 1 below, 50 parts by mass of an epoxy resin, 50 parts by mass of a hydroxynaphthalene novolac type phenol resin, and 0.1 parts by mass of 2-ethyl-4-methylimidazole are blended and dissolved in 400 parts by mass of propylene glycol monomethyl ether acetate. Then, it was filtered through a 0.2 μm membrane filter to prepare a resinous composition. The obtained resin composition was subjected to various evaluation tests in the following manner. The results are shown in Table 1.

Details of each component in Table 1 are as follows.
Epoxy resin (A'-1): “EPICOLON N-740” manufactured by DIC Corporation
Epoxy resin (A'-2): "EPICOLON N-655-EXP-S" manufactured by DIC Corporation

Evaluation of heat resistance The resin composition was applied onto a silicon wafer having a diameter of 5 inches using a spin coater, and heated at 180 ° C. for 60 seconds using a hot plate in an environment with an oxygen concentration of 20% by volume. Furthermore, it heated at 350 degreeC for 120 second, and obtained the silicon wafer with a resist film with a film thickness of 0.3 micrometer. The resist film was scraped from the silicon wafer and used as a test sample for heat resistance evaluation. Using a differential thermothermal gravimetric simultaneous measurement device (TG / DTA), the mass decrease when the temperature was raised under the following conditions was measured to determine the thermal decomposition starting temperature.
Measuring device: TG / DTA 6200 manufactured by Seiko Instruments Inc.
Measurement range: RT to 400 ° C
Temperature increase rate: 10 ° C / min Atmosphere: Nitrogen

Evaluation of dry etching resistance The resin composition was applied onto a silicon wafer having a diameter of 5 inches using a spin coater, and heated at 180 ° C. for 60 seconds using a hot plate in an environment with an oxygen concentration of 20% by volume. Furthermore, it heated at 350 degreeC for 120 second, and obtained the silicon wafer with a resist film with a film thickness of 0.3 micrometer. The formed resist film is CF ₄ / Ar / O ₂ (CF ₄ : 40 mL / min, Ar: 20 mL / min, O ₂ : 5 mL / min) using an etching apparatus (“EXAM” manufactured by Shinko Seiki Co., Ltd.) : 20 Pa RF power: 200 W Processing time: 40 seconds Temperature: 15 ° C.) Etching was performed. The film thickness before and after the etching treatment was measured to calculate the etching rate, and the etching resistance was evaluated. The evaluation criteria are as follows.
A: When the etching rate is 150 nm / min or less B: When the etching rate exceeds 150 nm / min

Claims (8)

1. A resin composition comprising an epoxy resin (A) having a polyarylene ether structure (α) and a hydroxynaphthalene novolac-type phenol resin (B).
2. The resin composition according to claim 1, wherein at least one of the aromatic nuclei in the polyarylene ether structure (α) has a naphthalene skeleton.
3. The resin composition according to claim 1, wherein the polyarylene ether structure (α) is a polynaphthylene ether structure.
4. The hydroxy naphthalene novolac type phenol resin (B) is represented by the following structural formula (1):
   

   

   (In the formula, l is 1 or 2, and the hydroxyl group may be bonded to any carbon atom on the naphthalene ring. R ¹ represents a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Each of R ² is independently an alkyl group, an alkoxy group, or a halogen atom, and may be bonded to any carbon atom on the naphthalene ring; m is 0 or an integer of 1 to 5.)
   An acyclic novolac resin (B1) having a structural moiety (β) represented by the following structural unit, and the following structural formula (2)
   

   

   [Wherein β is the structural moiety (β) represented by the structural formula (1), and n is an integer of 2 to 10. ]
   The resin composition according to claim 1, comprising a cyclic novolac resin (B2) having a molecular structure represented by:
5. The resin composition according to claim 1, wherein the number of moles of all epoxy groups in the resin composition is in the range of 0.01 to 0.8 moles with respect to 1 mole of all phenolic hydroxyl groups in the resin composition.
6. A cured product of the resin composition according to any one of claims 1 to 5.
7. A resist resin material comprising the resin composition according to any one of claims 1 to 5.
8. A resist film comprising the resin composition according to any one of claims 1 to 5.