KR102432123B1 - Phenolic hydroxyl group-containing resin and resist material - Google Patents

Abstract

(식 중 X는 탄소 원자수 1∼14의 탄화수소기를 나타낸다. R¹은 각각 독립으로 지방족 탄화수소기, 알콕시기, 할로겐 원자, 아릴기, 아랄킬기 중 어느 하나이다. m은 0, 1 또는 2, n은 0 또는 1∼4의 정수이다)
으로 표시되는 비스나프톨 화합물(a1)과 할로겐화시아누르(a2)와의 반응 생성물로서, 다분산도(Mw/Mn)가 1.01∼1.30의 범위인 페놀성 수산기 함유 수지를 제공한다.An object of the present invention to provide a phenolic hydroxyl group-containing resin having excellent fluidity and high heat resistance and dry etching resistance in a cured product, a curable composition containing the same, and a resist material, the structural formula (1)

(Wherein, X represents a hydrocarbon group having 1 to 14 carbon atoms. R ¹ is each independently any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. m is 0, 1 or 2, n is 0 or an integer from 1 to 4)
Provided is a phenolic hydroxyl group-containing resin having a polydispersity (Mw/Mn) in the range of 1.01 to 1.30 as a reaction product of a bisnaphthol compound (a1) represented by and a cyanuric halide (a2).

Description

Phenolic hydroxyl group-containing resin and resist material

The present invention relates to a phenolic hydroxyl group-containing resin having excellent fluidity and high heat resistance and dry etching resistance in a cured product, a curable composition containing the same, and a resist material.

In the field of photoresists, a variety of resist pattern formation methods subdivided according to uses and functions are being developed one after another, and with it, the performance required for a resin material for resist is also being advanced and diversified. For example, a resin material for pattern formation is required to have high developability for accurately forming fine patterns on highly integrated semiconductors and with high production efficiency. In applications called underlayer films, anti-reflection films, BARC films, hard masks, etc., dry etching resistance, low reflectivity, high fluidity that can cope with uneven substrate surfaces, etc. are required. Moreover, in the use called a resist permanent film etc., toughness, such as base material followability, in addition to high heat resistance is calculated|required. In addition, from the viewpoint of quality reliability, long-term storage stability under various environments around the world is also an important performance.

As one of the resin materials suitable for photoresists, a naphthol novolak-type resin is known (refer following patent document 1). The naphthol novolak-type resin is derived from a rigid naphthalene skeleton and has excellent dry etching resistance, but has low fluidity, so the coatability to the uneven substrate surface is low, and the surface smoothness of the resulting film is not sufficient.

Japanese Patent Laid-Open No. 2010-248435

Accordingly, the problem to be solved by the present invention is to provide a phenolic hydroxyl group-containing resin having excellent fluidity and high heat resistance and dry etching resistance in a cured product, a curable composition containing the same, and a resist material.

As a result of intensive studies conducted by the present inventors to solve the above problems, a phenolic hydroxyl group-containing resin having a polydispersity (Mw/Mn) in the range of 1.01 to 1.30 as a reaction product of a bisnaphthol compound and a cyanuric halide is It was discovered that it was excellent in the coating property to the surface of a base material which has unevenness|corrugation since fluidity|liquidity is high, and it is also excellent in the heat resistance and dry etching resistance in hardened|cured material, and came to complete this invention.

That is, the present invention, the following structural formula (1)

(Wherein, X represents a hydrocarbon group having 1 to 14 carbon atoms. R ¹ is each independently any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. m is 0, 1 or 2, n is 0 or an integer from 1 to 4)

It relates to a phenolic hydroxyl group-containing resin having a polydispersity (Mw/Mn) in the range of 1.01 to 1.30 as a reaction product of a bisnaphthol compound (a1) represented by and a cyanuric halide (a2).

The present invention also relates to a curable composition containing the phenolic hydroxyl group-containing resin and a curing agent.

The present invention also relates to a cured product of the curable composition.

The present invention also relates to a resist material using the curable composition.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in fluidity|liquidity, and a phenolic hydroxyl-containing resin with high heat resistance and dry etching resistance in a hardened|cured material, a curable composition containing this, and a resist material can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a GPC chart figure of phenolic hydroxyl-containing resin (1) obtained in Example 1. FIG.

The phenolic hydroxyl group-containing resin of the present invention has the following structural formula (1)

(Wherein, X represents a hydrocarbon group having 1 to 14 carbon atoms. R ¹ is each independently any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. m is 0, 1 or 2, n is 0 or an integer from 1 to 4)

It is a reaction product of a bisnaphthol compound (a1) represented by a cyanuric halide (a2), characterized in that the polydispersity (Mw/Mn) is in the range of 1.01 to 1.30.

The bisnaphthol compound (a1) can be obtained by, for example, a method of reacting a 2-naphthol compound with an aldehyde compound. The said 2-naphthol compound has a compound which has one or more substituents represented by R< ¹ > in said structural formula (1) on the aromatic nucleus of 2-naphthol or 2-naphthol, and may be used individually by 1 type, and 2 types You may use the above together.

R ¹ in Structural Formula (1) is each independently any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. Specific examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a vinyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, and a nonyl group. As a specific example of the said alkoxy group, a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, etc. are mentioned, for example. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a structural moiety in which the aliphatic hydrocarbon group, an alkoxy group, or a halogen atom is substituted on their aromatic nucleus. Specific examples of the aralkyl group include, for example, a phenylmethyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and a structural moiety in which the aliphatic hydrocarbon group, an alkoxy group, or a halogen atom is substituted on their aromatic nucleus. can Especially, since the heat resistance in hardened|cured material becomes still higher, it is preferable that both n and m in the said structural formula (1) are 0. That is, it is preferable to use 2-naphthol as a raw material for the reaction of the bisnaphthol compound (a1).

The aldehyde compound is, for example, formaldehyde, trioxane, acetaldehyde, propionaldehyde, tetraoxymethylene, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butylaldehyde, caproaldehyde , allylaldehyde, benzaldehyde, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, crotonaldehyde, acrolein, and the like. These may be used independently, respectively, and may use 2 or more types together. Among them, it is preferable to use formaldehyde because of its excellent reactivity. That is, it is preferable that X in the said structural formula (1) is a methylene group. Formaldehyde may be used as formalin in an aqueous solution state, may be used as paraformaldehyde in a solid state, or either may be used.

In the reaction of the 2-naphthol compound and the aldehyde compound, the target bisnaphthol compound (a1) is obtained in a high yield, so in the presence of an alkali catalyst, the temperature is gradually increased from room temperature, and the temperature is about 80 to 120 ° C. it is preferable You may perform reaction in an organic solvent as needed.

It is preferable that the reaction ratio of a 2-naphthol compound and an aldehyde compound is in the range used as 0.45-0.55 mol of an aldehyde compound with respect to 1 mol of 2-naphthol compound.

Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, and pyridine. These may be used independently, respectively, and may use 2 or more types together. It is preferable that the addition amount of an alkali catalyst is the range of 0.05-3 mass % with respect to the total mass of a reaction raw material.

The organic solvent is, for example, methanol, ethanol, propanol, butanol, ethyl lactate, 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, polyethylene glycol, glycerin, 2-ethoxyethanol, ethylene glycol mono Methyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether, diethylene glycol ethyl methyl ether , Propylene glycol monomethyl ether, 1,3-dioxane, 1,4-dioxane, tetrahydrofuran, ethylene glycol acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methylpyrrolidone , dimethylformamide, dimethyl sulfoxide, and the like. These solvents may be used independently, respectively, and may be used as 2 or more types of mixed solvent. Especially, since the said bisnaphthol compound (a1) is obtained in a high yield, alcohol solvents, such as methanol, ethanol, a propanol, and a butanol, are preferable. The organic solvent is preferably used in an amount of 0.5 to 5 times the total mass of the reaction raw material.

After completion of the reaction, the bisnaphthol compound (a1) with higher purity can be obtained by purifying the reaction product by washing with water, reprecipitation, or the like. The purity of the bisnaphthol compound (a1) is a phenolic hydroxyl group-containing resin excellent in the balance between heat resistance, dry etching resistance, and fluidity in the cured product. It is preferable, and it is more preferable that it is 99 % or more.

In addition, in this invention, the purity of the said bisnaphthol compound (a1) and content of each component in phenolic hydroxyl-containing resin are the values computed from the area ratio of the chart obtained by GPC measurement under the following conditions. In addition, the weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (Mw/Mn) of a hydroxyl-containing phenol resin are the values measured by GPC of the following conditions.

[Measurement conditions for GPC]

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation

Column: Showa Denko Co., Ltd. “Shodex KF802” (8.0 mmФ×300 mm) + Showa Denko Co., Ltd. “Shodex KF802” (8.0 mmФ×300 mm)+ Showa Denko Co., Ltd. “Shodex KF803” (8.0 mmФ×300 mm) manufactured by Kaisha + “Shodex KF804” manufactured by Showa Denko Co., Ltd. (8.0 mmФ × 300 mm)

Column temperature: 40℃

Detector: RI (Differential Refractometer)

Data processing: "GPC-8020 model II version 4.30" manufactured by Tosoh Corporation

Developing solvent: tetrahydrofuran

Flow rate: 1.0mL/min

Sample: A 0.5 mass % tetrahydrofuran solution in terms of resin solid content was filtered with a micro filter (100 μl)

Standard sample: the following monodisperse polystyrene

(Standard sample: monodisperse polystyrene)

"A-500" made by Tosoh Corporation

"A-2500" made by Tosoh Corporation

"A-5000" made by Tosoh Corporation

"F-1" made by Tosoh Corporation

"F-2" made by Tosoh Corporation

"F-4" made by Tosoh Corporation

"F-10" made by Tosoh Corporation

"F-20" made by Tosoh Corporation

The reaction method between the bisnaphthol compound (a1) and the cyanuric halide (a2) is not particularly limited, and for example, a method of reacting in the presence of a hydrogen halide scavenger under a temperature condition of about 50 to 100 ° C. have. You may perform reaction in an organic solvent as needed.

The reaction ratio of the bisnaphthol compound (a1) and the cyanuric halide (a2) is easy to adjust the polydispersity (Mw/Mn) of the resulting phenolic hydroxyl group-containing resin within the range of 1.0 to 1.5, so the molar ratio [ (a1)/(a2)] is preferably in the range of 1.5 to 5, more preferably in the range of 2.0 to 3.5.

As the hydrogen halide scavenger, for example, a basic compound such as a tertiary amine compound such as trimethylamine or triethylamine, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an alkali metal carbonate of sodium carbonate or potassium carbonate can be used. have. It is preferable to use these addition amounts in the range of 1-2 mol with respect to 1 mol of the said cyanuric halide (a2).

The organic solvent is preferably a hydrophobic solvent, and examples thereof include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic hydrocarbon solvents such as benzene, toluene and xylene. The organic solvent is preferably used in an amount of 0.5 to 5 times the total mass of the reaction raw material.

After completion of the reaction, the reaction product is washed with water to remove the produced salt. Since the phenolic hydroxyl group-containing resin of the present invention has further excellent balance between heat resistance, dry etching resistance and fluidity in the cured product, the content of the component having a number average molecular weight (Mn) of 500 or less is shown in the GPC chart. The value calculated from the area ratio of is preferably in the range of 0.1 to 3.0%, more preferably in the range of 0.1 to 2.8%, and particularly preferably in the range of 0.3 to 2.0%. Content of the component whose number average molecular weight (Mn) is 500 or less can be adjusted by increasing the frequency|count of water washing, or performing reprecipitation.

The phenolic hydroxyl group-containing resin of the present invention has the following structural formula (2)

(Wherein, X represents a hydrocarbon group having 1 to 14 carbon atoms. R ¹ is each independently any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. m is 0, 1 or 2, n is 0 or an integer from 1 to 4)

It is preferable to contain the polynuclear compound (A) represented as an essential component. The content of the polynuclear compound (A) is 35 as a value calculated from the area ratio in the GPC chart, since the cured product has a phenolic hydroxyl group-containing resin that has a much better balance between heat resistance, dry etching resistance, and fluidity. % or more, more preferably in the range of 35 to 90%, and particularly preferably in the range of 55 to 80%.

In the phenolic hydroxyl group-containing resin of the present invention, in addition to the polynuclear compound (A) represented by the structural formula (1), for example, a part or all of the phenolic hydroxyl groups in the structural formula (1) have the following structural formula (3)

(Wherein, X represents a hydrocarbon group having 1 to 14 carbon atoms. R ¹ is each independently any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. m is 0, 1 or 2, n is 0 or an integer from 1 to 4)

You may contain the component etc. substituted by the structural moiety represented by. In particular, since the heat resistance and dry etching resistance of the cured product are further excellent, in addition to the polynuclear compound (A), one of the phenolic hydroxyl groups in the structural formula (1) is substituted with the structural formula (3) ( B) is preferred. At this time, the total content of the polynuclear compound (A) and the compound (B) in the phenolic hydroxyl group-containing resin is a value calculated from the area ratio of the GPC chart, preferably in the range of 50 to 99%, and from 60 to It is more preferable that it is the range of 99%, and it is especially preferable that it is the range of 80-99%.

It is preferable that the weight average molecular weight (Mw) of phenolic hydroxyl group containing resin of this invention measured by GPC of the said conditions is the range of 980-1,200. In addition, although the phenolic hydroxyl group-containing resin of the present invention is characterized in that the polydispersity (Mw/Mn) is in the range of 1.01 to 1.30, the balance between heat resistance and dry etching resistance and fluidity in the cured product is further improved. Since it becomes excellent phenolic hydroxyl-containing resin, it is more preferable that the range of polydispersity (Mw/Mn) is 1.01 - 1.25, It is especially preferable that it is the range of 1.01 - 1.20.

The phenolic hydroxyl group containing resin of this invention mentioned above can be used for various uses, such as a paint, an adhesive agent, an electrical/electronic member, a photoresist, and a liquid crystal aligning film, similarly to a general phenol resin.

The curable composition of this invention contains the said phenolic hydroxyl-containing resin of this invention, and a hardening|curing agent as essential components. The curable composition of this invention may contain other resin (C) other than the phenolic hydroxyl group containing resin of the said this invention. Other resins (C) used herein include, for example, various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, and phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatics. Modified with compound Novolak resin, phenol aralkyl resin (xylok resin), naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, aminotriazine-modified A phenol resin, various vinyl polymers, etc. are mentioned.

More specifically, the various novolac resins include phenol, alkylphenol such as cresol and xylenol, phenylphenol, resorcinol, biphenyl, bisphenol such as bisphenol A and bisphenol F, naphthol, dihydroxynaphthalene, etc. and a polymer obtained by reacting a phenolic hydroxyl group-containing compound with an aldehyde compound under acid catalyst conditions.

The various vinyl polymers include polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, Homopolymers of vinyl compounds, such as polynortricylene and poly(meth)acrylate, or these copolymers are mentioned.

When these other resins are used, the blending ratio of the phenolic hydroxyl group-containing resin of the present invention and other resins (C) can be arbitrarily set according to the use, but the effect of excellent heat resistance exhibited by the present invention is more pronounced. , It is preferable that it is a ratio used as 0.5-100 mass parts of other resin (C) with respect to 100 mass parts of phenolic hydroxyl group containing resin of this invention.

The curing agent used in the present invention is not particularly limited as long as it is a compound capable of generating a curing reaction with the phenolic hydroxyl group-containing resin of the present invention, and various compounds can be used. In addition, the curing method of the curable composition of this invention is not specifically limited, According to the kind of hardening agent, the kind of hardening accelerator mentioned later, etc., it can harden by suitable methods, such as thermosetting and photocuring. Curing conditions, such as heating temperature and time in thermosetting, the kind of light in photocuring, exposure time, etc. are suitably adjusted according to the kind of hardening|curing agent, the kind of hardening accelerator mentioned later, etc.

Specific examples of the curing agent include, for example, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, a resol resin, an epoxy compound, an isocyanate compound, an azide compound, a compound containing a double bond such as an alkenyl ether group , an acid anhydride, an oxazoline compound, and the like.

The melamine compound is, for example, hexamethylolmelamine, hexamethoxymethylmelamine, a compound in which 1 to 6 methylol groups of hexamethylolmelamine are methoxymethylated, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, The compound etc. which 1-6 of the methylol groups of hexamethylolmelamine carried out acyloxymethylation are mentioned.

The guanamine compound is, for example, tetramethylol guanamine, tetramethoxymethyl guanamine, tetramethoxymethyl benzo guanamine, tetramethylol guanamine 1-4 methylol groups of methoxymethylated compounds, The compound etc. which acyloxymethylated 1-4 methylol groups of tetramethoxyethyl guanamine, tetraacyloxy guanamine, and tetramethylol guanamine are mentioned.

The glycoluril compound is, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3, 4,6-tetrakis(hydroxymethyl)glycoluril etc. are mentioned.

The urea compound is, for example, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(meth oxymethyl) urea and the like.

The resol resin is, for example, phenol, alkylphenol such as cresol or xylenol, phenylphenol, resorcinol, biphenyl, bisphenol such as bisphenol A or bisphenol F, naphthol, and phenolic properties such as dihydroxynaphthalene. The polymer obtained by making a hydroxyl-containing compound and an aldehyde compound react under alkaline catalyst conditions is mentioned.

The epoxy compound is, for example, diglycidyloxynaphthalene, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol coaxial novolak type epoxy resin, naphthol-cresol Coaxial novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, 1,1-bis(2,7-diglycidyloxy-1-naphthyl) alkane, naphthylene ether type epoxy resin, tri phenylmethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phosphorus atom containing epoxy resin, polyglycidyl ether of cocondensate of phenolic hydroxyl group containing compound and alkoxy group containing aromatic compound, etc. are mentioned. .

As for the said isocyanate compound, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate etc. are mentioned, for example.

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

The compound containing a double bond, such as an alkenyl ether group, is, for example, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, and 1,4-butanediol divinyl. Ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylol propane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol Tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylol propane trivinyl ether, etc. are mentioned.

The acid anhydride is, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4,4'- aromatic acid anhydrides such as (isopropylidene)diphthalic anhydride and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride; and alicyclic carboxylic acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride decenylsuccinic anhydride, and trialkyltetrahydrophthalic anhydride. .

Among these, since it becomes a curable composition excellent in sclerosis|hardenability and heat resistance in hardened|cured material, a glycoluril compound, a urea compound, and a resol resin are preferable, and a glycoluril compound is especially preferable.

Since the compounding quantity of the said hardening|curing agent in the curable composition of this invention becomes a composition excellent in curability, it is 0.5-50 mass parts with respect to a total of 100 mass parts of the phenolic hydroxyl-containing resin of this invention and other resin (C). It is preferable that it is a ratio.

The curable composition of this invention may contain a hardening accelerator according to the said hardening|curing agent. When thermosetting the curable composition of the present invention, an acid compound such as acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate and manganese acetate is preferably used as the curing accelerator. On the other hand, when photocuring the curable composition of the present invention, it is preferable to use a photoacid generator as a curing accelerator. Examples of the photoacid generator include sulfonium salt compounds such as tris(4-methylphenyl)sulfonium trifluoromethanesulfonate and tris(4-methylphenyl)sulfonium hexafluorophosphate; Bis[4-n-alkylphenyl]iodonium hexafluorophosphate, bis[4-n-alkylphenyl]iodonium hexafluoroantimonate, bis(4-t-butylphenyl)iodonium hexafluoro Iodo such as lophosphate, bis(4-t-butylphenyl)iodoniumbis(perfluorobutanesulfonyl)imide, and bis[4-n-alkylphenyl]iodoniumtetrakispentafluorophenylborate nium salt compounds (the n-alkyl group in each compound preferably has 10 to 13 carbon atoms); 2-[2-(furan-2-yl)ethynyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(methylfuran-2-yl)ethynyl]-4 ,6-bis(trichloromethyl)-s-triazine, 2-(methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-methoxyphenyl) ) ethynyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethynyl] -4,6-bis (trichloromethyl) - Chloromethyltriazine compounds, such as s-triazine, etc. are mentioned. A hardening accelerator may be used individually, respectively, and may use 2 or more types together. It is preferable that the addition amount of a hardening accelerator is the range used as 0.1-10 mass % with respect to the sum total of the resin component and hardening|curing agent component in a curable composition.

The curable composition of this invention may be diluted with the organic solvent. Although the organic solvent to be used is not specifically limited, For example, 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. ether; dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; alkylene glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl 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-methoxy ester compounds such as butyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate, and ethyl lactate; You may use two or more types together.

As described above, the phenolic hydroxyl group-containing resin of the present invention can be used in various applications such as paints, adhesives, electrical/electronic members, photoresists, and liquid crystal aligning films. It is particularly suitable for resist materials, and can be used for various resist members such as resist underlayer films and resist permanent films in addition to general interlayer insulating films.

When the phenolic hydroxyl group-containing resin of the present invention is used for a resist material, the method of use thereof is varied. For example, a method of using as a positive photoresist material such as in combination with a photosensitive agent, or a method of using a thermosetting agent in combination with a curing agent The method of using it as a resin material of , the method of using as a negative photoresist material in combination with a hardening|curing agent and a photosensitive hardening accelerator, etc. are mentioned. Among them, a method of using as a thermosetting resin material in combination with a curing agent by utilizing the characteristics of excellent fluidity and high heat resistance and dry etching resistance in the cured product, or a negative type photo in combination with a curing agent and a photosensitive curing accelerator The method used as a resist material is preferable.

The photosensitizer is, for example, an aromatic (poly)hydroxy compound, naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, orthoquinone-1,2-diazide-4-sulfonic acid The compound etc. which have quinone diazide groups, such as an ester compound with sulfonic acid which have quinone diazide groups, such as anthraquinone diazide sulfonic acid, or amidate, etc. are mentioned.

When the phenolic hydroxyl group-containing resin of the present invention is used for positive photoresist applications, the phenolic hydroxyl group-containing resin of the present invention, other resins (C), a photosensitizer, and other additives are blended and dissolved in an organic solvent A composition for positive photoresists can be prepared by mixing with a stirrer or the like. When containing a filler or a pigment, it is preferable to disperse|distribute or mix using dispersing apparatuses, such as a dissolver, a homogenizer, and a three-roll mill.

As an example of photolithography using the composition for positive photoresist, for example, the composition for positive photoresist is applied on an object to be subjected to photolithography such as a silicon substrate, a silicon carbide substrate, a gallium nitride base, and 60 to Prebaking is carried out at a temperature condition of 150°C. Next, after exposing through a resist pattern, a resist pattern is produced by dissolving an exposure part with an alkali developer.

When the curable composition of the present invention is used for a resist underlayer film, the phenolic hydroxyl group-containing resin of the present invention, other resins (C), a curing agent, a curing accelerator, and other additives are blended and dissolved in an organic solvent. The composition for resist underlayer films can be manufactured by mixing using , a stirrer, etc. When containing a filler or a pigment, it is preferable to disperse|distribute or mix using dispersing apparatuses, such as a dissolver, a homogenizer, and a three-roll mill.

As an example of a method of creating a resist underlayer film from the resist underlayer film composition, for example, the resist underlayer film composition is applied onto an object subjected to photolithography such as a silicon substrate, a silicon carbide substrate, a gallium nitride substrate, and 100 to 200 After drying under a temperature condition of deg. C, a resist underlayer film is formed by a method such as heat curing under a temperature condition of 250 to 400 deg. Next, a resist pattern is formed by performing a normal photolithography operation on this underlayer film, and dry etching treatment is performed with a halogen-based plasma gas or the like, whereby a resist pattern by the multilayer resist method can be formed.

When the curable composition of the present invention is used for a permanent resist film application, the phenolic hydroxyl group-containing resin of the present invention, other resins (C), a curing agent, a curing accelerator, and other additives are blended and dissolved in an organic solvent. The composition for resist underlayer films can be manufactured by mixing using , a stirrer, etc. When containing a filler or a pigment, it is preferable to disperse|distribute or mix using dispersing apparatuses, such as a dissolver, a homogenizer, and a three-roll mill.

As an example of photolithography using the composition for a permanent resist film, for example, the composition for a permanent resist film is applied on an object subjected to photolithography such as a silicon substrate, a silicon carbide substrate, a gallium nitride substrate, and the like, and a temperature condition of 60 to 150° C. prebaked in Next, after generating an acid with light through the resist pattern, it is thermosetted at a temperature of 110 to 210°C, and the unexposed portion is dissolved with an alkali developer to form a resist pattern. The permanent film made of the composition for a resist permanent film is, for example, in a semiconductor device relationship, a solder resist, a package material, an underfill material, a package adhesive layer such as a circuit element, an adhesive layer between an integrated circuit element and a circuit board, and a thin type represented by LCD and OELD. In a display relation, it can be suitably used for a thin film transistor protective film, a liquid crystal color filter protective film, a black matrix, a spacer, etc.

(Example)

Hereinafter, the present invention will be described in more detail by giving specific examples.

In a present Example, the purity of a compound and content of each component in resin are the values computed from the area ratio of the chart figure obtained by GPC measurement under the following conditions. In addition, the weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (Mw/Mn) of resin are the values measured by GPC of the following conditions.

[Measurement conditions for GPC]

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation

Column: Showa Denko Co., Ltd. “Shodex KF802” (8.0 mmФ×300 mm) + Showa Denko Co., Ltd. “Shodex KF802” (8.0 mmФ×300 mm)

+ 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℃

Detector: RI (Differential Refractometer)

Data processing: "GPC-8020 model II version 4.30" manufactured by Tosoh Corporation

Developing solvent: tetrahydrofuran

Flow rate: 1.0mL/min

Sample: A 0.5 mass % tetrahydrofuran solution in terms of resin solid content was filtered with a micro filter

Injection volume: 0.1mL

Standard sample: the following monodisperse polystyrene

(Standard sample: monodisperse polystyrene)

"A-500" made by Tosoh Corporation

"A-2500" made by Tosoh Corporation

"A-5000" made by Tosoh Corporation

"F-1" made by Tosoh Corporation

"F-2" made by Tosoh Corporation

"F-4" made by Tosoh Corporation

"F-10" made by Tosoh Corporation

"F-20" made by Tosoh Corporation

Preparation Example 1 Preparation of bisnaphthol compound (a1)

600 mass parts of isopropyl alcohol, 576 mass parts of 2-naphthol, 144 mass parts of 41.5% formalin, and 10 mass parts of 48% sodium hydroxide aqueous solution were thrown into the 2000 ml four-necked flask which installed the cooling tube. After raising the temperature from room temperature (about 25°C) to 100°C over 2 hours while stirring, stirring was continued for 3 hours while refluxing. After cooling to room temperature, the precipitated reaction product was filtered off under reduced pressure with Nutsie, and the cake-like residue was washed 5 times with 500 parts by mass of ion-exchanged water. The obtained cake was vacuum-dried at 80 degreeC for 72 hours, and 550 mass parts of white bisnaphthol compounds (a1) were obtained. The number average molecular weight (Mn) of the obtained bisnaphthol compound (a1) was 351, the weight average molecular weight (Mw) was 352, and the polydispersity (Mw/Mn) was 1.00.

Example 1 Preparation of phenolic hydroxyl group-containing resin (1)

152 parts by mass of the bisnaphthol compound (a1) obtained above, 31 parts by mass of cyanuric chloride, and 500 parts by mass of methyl ethyl ketone were put into a attached 1000 ml four-neck flask equipped with a cooling tube, and dissolved by stirring. 52 mass parts of triethylamines were dripped over 60 minutes, heating about 50 degreeC - 70 degreeC. Stirring was continued at 70 degreeC after completion|finish of dripping for 5 hours. Next, 200 mass parts of water was added, triethylamine hydrochloride was dissolved, it liquid-separated, and the water layer was rejected. Further, after washing twice with the same amount of water, methyl ethyl ketone is recovered by distillation, reprecipitation operation is performed twice with a mixed solvent of methanol/water = 10/1 (mass ratio), and the precipitate is recovered and dried under reduced pressure, 113 parts by mass of phenolic hydroxyl group-containing resin (1) was obtained. The obtained phenolic hydroxyl group-containing resin (1) has a number average molecular weight (Mn) of 963, a weight average molecular weight (Mw) of 1,050, a polydispersity (Mw/Mn) of 1.09, and a number average molecular weight (Mn) of 500 or less components The content was 0.8%. In addition, the content of the polynuclear compound (A) in the phenolic hydroxyl group-containing resin (1) was 59.2%, and the total content of the polynuclear compound (A) and the compound (B) was 85.5%. The GPC chart figure of phenolic hydroxyl group containing resin (1) is shown in FIG.

Example 2 Preparation of phenolic hydroxyl group-containing resin (2)

Except having changed the addition amount of the bisnaphthol compound (a1) from 152 mass parts to 114 mass parts in Example 1, it carried out similarly to Example 1, and obtained 92 mass parts of phenolic hydroxyl-containing resin (2). The obtained phenolic hydroxyl group-containing resin (2) has a number average molecular weight (Mn) of 1,013, a weight average molecular weight (Mw) of 1,252, a polydispersity (Mw/Mn) of 1.24, and a number average molecular weight (Mn) of 500 or less components The content was 2.8%. The content of the polynuclear compound (A) in the phenolic hydroxyl group-containing resin (2)) was 37.9%, and the total content of the polynuclear compound (A) and the compound (B) was 61.5%.

Comparative Preparation Example 1 Preparation of phenolic hydroxyl group-containing resin (1')

144 parts by mass of 2-naphthol, 400 parts by mass of n-butanol, 96 parts by mass of water, and 27.7 parts by mass of 92% paraformaldehyde were charged to a 1 L four-neck flask equipped with a thermometer, a cooling tube and a stirrer. Continuing stirring, 2.4 mass parts of para-toluenesulfonic acid monohydrate was added. Then, it heated up to 100 degreeC, stirring, and was made to react for 2 hours. After completion of the reaction, 200 parts by mass of n-butanol was added, and the solution in the system was washed with water until the washing water became neutral, and then the solvent was removed from the organic layer under heating and reduced pressure to obtain 153 g of a phenolic hydroxyl group-containing resin (1'). GPC of the phenolic hydroxyl group-containing resin (1') has a number average molecular weight (Mn) = 955, a weight average molecular weight (Mw) = 1,427, a polydispersity (Mw/Mn) = 1.49, and a component content rate of 500 or less with Mn of 5.2 mass was %.

Comparative Preparation Example 2 Preparation of phenolic hydroxyl group-containing resin (2')

152 parts by mass of the bisnaphthol compound (a1) obtained above, 31 parts by mass of cyanuric chloride, and 500 parts by mass of methyl ethyl ketone were put into a attached 1000 ml four-neck flask equipped with a cooling tube, and dissolved by stirring. 52 mass parts of triethylamines were dripped over 60 minutes, heating about 50 degreeC - 70 degreeC. After completion of dripping, stirring was continued at 70 degreeC for 5 hours. Next, 200 mass parts of water was added, triethylamine hydrochloride was dissolved, it liquid-separated, and the water layer was rejected. Furthermore, after washing with water twice with the same amount of water, methyl ethyl ketone was collect|recovered by distillation, it dried under reduced pressure, and 124 mass parts of phenolic hydroxyl-containing resin (2') was obtained. The number average molecular weight (Mn) of the obtained phenolic hydroxyl group-containing resin (2') is 958, the weight average molecular weight (Mw) is 1,258, the polydispersity (Mw/Mn) is 1.31, and the number average molecular weight (Mn) is 500 or less. The content of was 12.3%. The content of the polynuclear compound (A) in the phenolic hydroxyl group-containing resin (1) was 51.4%, and the total content of the polynuclear compound (A) and the compound (B) was 72.0%.

Examples 3 and 4 and Comparative Examples 1 and 2

The phenolic hydroxyl group-containing resin obtained in Examples 1 and 2 and Comparative Production Examples 1 and 2 was evaluated in the following manner. A result is shown in Table 1.

Preparation of thermosetting composition

1.6 parts by mass of a phenolic hydroxyl group-containing resin, 0.4 parts by mass of a curing agent (“1,3,4,6-tetrakis(methoxymethyl)glycoluril” manufactured by Tokyo Chemical Industry Co., Ltd.), 0.1 parts by mass of para-toluenesulfonic acid Part was dissolved in 100 parts by mass of propylene glycol monomethyl ether acetate, and this was filtered through a 0.2 µm membrane filter to obtain a thermosetting composition.

Evaluation of sublimation resistance

The thermosetting composition obtained above was applied on a 5-inch silicon wafer by a spin coater, and dried for 180 seconds on a hot plate at 110° C. in an environment with an oxygen concentration of 20% by volume. Next, it heat-hardened at 210 degreeC for 60 second, and obtained the cured coating film with a film thickness of 0.3 micrometer. The mass of the wafer was measured before and after the hardening process at 210 degreeC, the mass decrease in the hardening process was computed, and the following reference|standard evaluated.

A: The amount of mass decrease in the curing process at 210°C for 60 seconds is 3% or less

B: The amount of mass loss in the curing process at 210°C for 60 seconds exceeds 3%

Evaluation of heat resistance

The thermosetting composition obtained above was applied on a 5-inch silicon wafer by a spin coater, and dried for 180 seconds on a hot plate at 110° C. in an environment with an oxygen concentration of 20% by volume. Next, it heat-hardened at 210 degreeC for 60 second, and obtained the cured coating film with a film thickness of 0.3 micrometer. The obtained cured coating film was scraped off from the wafer, and the amount of mass loss at 240° C. when the temperature was raised under the following conditions was measured using a differential thermogravimetric simultaneous measurement apparatus (TG/DTA), and evaluated according to the following criteria.

[Conditions for measuring mass loss]

Measuring device: Seiko Instruments "TG/DTA 6200"

Measurement range: room temperature to 400℃

Temperature increase rate: 10℃/min

[Evaluation standard]

A: The amount of mass decrease at 240°C is 5% by mass or less

B: The mass decrease at 240°C exceeds 5% by mass

Assessment of liquidity

On a silicon wafer having a diameter of 5 inches on which a hole pattern having a diameter of 110 nm and a depth of 300 nm was formed, the thermosetting composition obtained above was applied by a spin coater, and dried for 180 seconds on a hot plate at 110° C. in an environment with an oxygen concentration of 20% by volume. After making it, it heat-hardened at 210 degreeC for 60 second, and obtained the cured coating film with a film thickness of 0.3 micrometer. The silicon wafer was cut on the hole pattern line, the cross section was observed with a laser microscope ("VK-X200" manufactured by Keyence Corporation), and whether or not the inflow of the curable composition into the hole pattern was sufficient was evaluated under the following conditions. .

A: The whole hole is filled with hardened material

B: When the entire hole is not filled with cured material and there are voids

Dry etching resistance evaluation

It carried out similarly to evaluation of heat resistance, and provided the cured coating film on a silicon wafer. The cured coating film on the wafer was CF ₄ /Ar/O ₂ (CF ₄ : 40 mL/min, Ar: 20 mL/min, O ₂ : 5 mL/min pressure) using an etching apparatus (“EXAM” manufactured by Shinko Seiki Corporation). : 20 Pa RF power: 200 W Treatment time: 40 seconds The etching process was performed under the conditions of temperature: 15 degreeC). The film thickness before and after the etching process at this time was measured, the etching rate was computed, and 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

[Table 1]

Examples 5 and 6, Comparative Examples 3 and 4

The phenolic hydroxyl group-containing resin obtained in Examples 1 and 2 and Comparative Production Examples 1 and 2 was evaluated in the following manner. A result is shown in Table 2.

Preparation of photocurable composition

1.6 parts by mass of a phenolic hydroxyl group-containing resin, 0.4 parts by mass of a curing agent (“1,3,4,6-tetrakis(methoxymethyl)glycoluril” manufactured by Tokyo Chemical Industry Co., Ltd.), 0.2 parts by mass of a photoacid generator It was melt|dissolved in 100 mass parts of propylene glycol monomethyl ether acetate, this was filtered with a 0.2-micrometer membrane filter, and the thermosetting composition was obtained.

The photo-acid generator was manufactured by Sanwa Chemical Co., Ltd. "TFE-triazine" (2-[2-(furan-2-yl)ethynyl]-4,6-bis(trichloromethyl)-s-triazine) used

Evaluation of alkali developability [ADR (nm/s)]

The photosensitive composition obtained above was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 μm, and dried for 60 seconds on a hot plate at 110°C. After immersing this in an alkaline developing solution (2.38% tetramethylammonium hydroxide aqueous solution) for 60 second, it dried for 60 second on a 110 degreeC hotplate. The film thickness before and after immersion in a developer was measured, and the value obtained by dividing the difference by 60 was defined as alkali developability [ADR (nm/s)].

Evaluation of photosensitivity

The photosensitive composition obtained above was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 μm, and dried for 60 seconds on a hot plate at 110°C. On this wafer, a mask corresponding to a resist pattern having a line and space ratio of 1:1 and a line width of 1 to 10 μm set for every 1 μm was adhered, followed by a ghi line lamp (“Multilite” manufactured by Ushio Denki Co., Ltd.) ) was used to irradiate the ghi line, and heat treatment was performed at 140°C for 60 seconds. Next, after being immersed for 60 seconds in an alkali developer (2.38% aqueous solution of tetramethylammonium hydroxide), it was dried for 60 seconds on a hot plate at 110°C.

The exposure dose (Eop dose) capable of faithfully reproducing a line width of 3 µm when the ghi line exposure dose was increased from 30 mJ/cm 2 to every 5 mJ/cm 2 was evaluated.

evaluation of resolution

The photosensitive composition obtained above was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 μm, and dried for 60 seconds on a hot plate at 110°C. A photomask was placed on the obtained wafer, irradiated with 200 mJ/cm 2 of ghi line, and cured at 210°C for 180 seconds, followed by alkali development. The state of the pattern was confirmed using a laser microscope ("VK-X200" manufactured by Co., Ltd.), A was resolved at L/S = 5 µm, and B was not resolved at L/S = 5 µm. evaluated as

[Table 2]

Claims (7)

The following structural formula (1)

(Wherein, X represents a hydrocarbon group having 1 to 14 carbon atoms. R ¹ is each independently any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. m is 0, 1 or 2, n is 0 or an integer from 1 to 4)
A phenolic hydroxyl group-containing resin that is a reaction product of a bisnaphthol compound (a1) and a cyanuric halide (a2) represented by
polydispersity (Mw/Mn) is in the range of 1.01 to 1.30,
Phenolic hydroxyl group containing resin whose content of the component whose number average molecular weight (Mn) is 500 or less is 0.1 to 3.0% of the range by the value computed from the area ratio of a GPC chart figure. delete According to claim 1,
The following structural formula (2)

(Wherein, X represents a hydrocarbon group having 1 to 14 carbon atoms. R ¹ is each independently any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. m is 0, 1 or 2, n is 0 or an integer from 1 to 4)
A phenolic hydroxyl group-containing resin containing the polynuclear compound (A) represented as an essential component, wherein the content of the polynuclear compound (A) is 35% or more as a value calculated from the area ratio in the GPC chart. According to claim 1,
The following structural formula (2)

(Wherein, X represents a hydrocarbon group having 1 to 14 carbon atoms. R ¹ is each independently any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. m is 0, 1 or 2, n is 0 or an integer from 1 to 4)
The polynuclear compound (A) represented by and one of the phenolic hydroxyl groups in the structural formula (2) have the following structural formula (3)

(Wherein, X represents a hydrocarbon group having 1 to 14 carbon atoms. R ¹ is each independently any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. m is 0, 1 or 2, n is 0 or an integer from 1 to 4)
A phenolic hydroxyl group-containing resin containing the compound (B) substituted with , as an essential component, and the total content of both is in the range of 50 to 99% as a value calculated from the area ratio of the GPC chart. A curable composition comprising the phenolic hydroxyl group-containing resin according to any one of claims 1 to 4 and a curing agent. A cured product of the curable composition according to claim 5. 6. The method of claim 5,
A curable composition which is a resist material.

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