TW201833161A - Resin containing phenolic hydroxy group and resist material - Google Patents

Abstract

Provided are: a resin containing phenolic hydroxy groups which is high in flowability and heat resistance and which, when used as a resist material, is excellent in terms of developability and dry-etching resistance; and a photosensitive composition, a curable composition, and a resist material each containing the resin containing phenolic hydroxy groups. Specifically, use is made of a resin containing phenolic hydroxy groups which is a product of the reaction of a compound (A) represented by structural formula (1) with an aldehyde compound (B). [In formula (1), the Ar1 moieties are each independently an optionally substituted aryl group and at least one of the Ar1 moieties includes an aromatic ring having a hydroxy group thereon; R1 is a hydrogen atom or an aliphatic hydrocarbon group; R2 is an optionally substituted aliphatic hydrocarbon group, an alkoxy group, or a halogen atom; and n is 0 or an integer of 1-4.].

Description

 Phenolic hydroxyl-containing resin and resist material  

The present invention relates to a phenolic hydroxyl group-containing resin excellent in developability or dry etching resistance in the case where the fluidity and heat resistance are high and used as a resist material, a photosensitive composition containing the same, and a hardenability. Composition, and resist material.

In the field of photoresists, a variety of resist pattern forming methods which are subdivided according to the use or function are continuously developed, and the required performance of the resin material for resists is also increased and diversified. For example, in the resin material for pattern formation, in order to form a fine pattern on a highly integrated semiconductor with high precision and high productivity, high developability is required. In applications called underlayer films, antireflection films, BARC films, hard masks, etc., dry etching resistance, low reflectivity, or high fluidity of the surface of the substrate having irregularities are required. Further, in applications called a resist permanent film or the like, in addition to high heat resistance, toughness such as substrate followability is also required. Furthermore, in terms of quality reliability, long-term storage stability in various environments around the world is also an important performance.

The most widely used phenolic phenol-based resin cresol novolak type for photoresist applications, but it is not suitable for the current market demand performance that is highly advanced and diversified, so it is heat-resistant, fluid, and developed. Further improvement is made in various performances such as properties or dry etching resistance (see Patent Document 1).

 [Previous Technical Literature]    [Patent Literature]  

[Patent Document 1] Japanese Patent Laid-Open No. 2-55359

The object of the present invention is to provide a phenolic hydroxyl group-containing resin which is excellent in fluidity and heat resistance and which is excellent in developability or dry etching resistance when used as a resist material, and contains photosensitivity thereof. A composition, a curable composition, and a resist material.

In order to solve the above problems, the inventors of the present invention have found that a resin containing a phenolic hydroxyl group, which is a reaction product of a compound represented by the following structural formula (1) and an aldehyde compound, has high fluidity and heat resistance. It is also excellent in developability or dry etching resistance when used as a resist material, and the present invention has been completed.

[wherein Ar ^{1 is} each independently an aryl group which may have a substituent, and at least one of Ar ¹ has a hydroxyl group on the aromatic ring. R ¹ is a hydrogen atom or an aliphatic hydrocarbon group. R ² may be any of an aliphatic hydrocarbon group, an alkoxy group or a halogen atom which may have a substituent, and n is 0 or an integer of 1 to 4]

That is, the present invention relates to a phenolic hydroxyl group-containing resin which is a reactant of the compound (A) represented by the following structural formula (1) and an aldehyde compound (B).

[wherein Ar ^{1 is} each independently an aryl group which may have a substituent, and at least one of Ar ¹ has a hydroxyl group on the aromatic ring. R ¹ is a hydrogen atom or an aliphatic hydrocarbon group. R ² may be any of an aliphatic hydrocarbon group, an alkoxy group or a halogen atom which may have a substituent, and n is 0 or an integer of 1 to 4]

Further, the present invention relates to a photosensitive composition comprising the above phenolic hydroxyl group-containing resin and a sensitizer.

Further, the present invention relates to a curable composition comprising the above phenolic hydroxyl group-containing resin and a curing agent.

Further, the present invention relates to a cured product of the above curable composition.

Further, the present invention relates to a resist material using the above phenolic hydroxyl group-containing resin.

According to the present invention, it is possible to provide a phenolic hydroxyl group-containing resin which is excellent in fluidity and heat resistance and which is excellent in developability or dry etching resistance when used as a resist material, and a photosensitive composition containing the same. A curable composition and a resist material.

Fig. 1 is a GPC chart of the compound (A-1) obtained in Production Example 1.

Fig. 2 is a ¹³ C-NMR chart of the compound (A-1) obtained in Production Example 1.

Fig. 3 is a GPC line diagram of the phenolic hydroxyl group-containing resin (1) obtained in Example 1.

Fig. 4 is a GPC line diagram of the phenolic hydroxyl group-containing resin (2) obtained in Example 2.

Hereinafter, the present invention will be described in detail.

The phenolic hydroxyl group-containing resin of the present invention is a reaction product of the compound (A) represented by the following structural formula (1) and the aldehyde compound (B).

[wherein Ar ^{1 is} each independently an aryl group which may have a substituent, and at least one of Ar ¹ has a hydroxyl group on the aromatic ring. R ¹ is a hydrogen atom or an aliphatic hydrocarbon group. R ² may be any of an aliphatic hydrocarbon group, an alkoxy group or a halogen atom which may have a substituent, and n is 0 or an integer of 1 to 4]

Ar ¹ in the above structural formula (1) is each independently an aryl group which may have a substituent, and at least one of Ar ¹ has a hydroxyl group on the aromatic ring. Specifically, the aryl group which may have a substituent means that, in addition to a phenyl group, a naphthyl group, an anthracenyl group, one or more hydroxyl groups, an aliphatic hydrocarbon group, an alkoxy group, and a halogen may be mentioned in the aromatic nucleus. A structural part of a substituent such as an atom. The aliphatic hydrocarbon group may be either a linear one or a branched structure, or may be one having an unsaturated group in the structure and no unsaturated group in the structure. The number of carbon atoms is not particularly limited, and may be any one of a short chain having 1 to 6 carbon atoms or a relatively long chain having 7 or more carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and a cyclohexyloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. In particular, in the case of a resin having a phenolic hydroxyl group which is excellent in alkali developability, sensitivity, resolution, and the like in the case of a resist application, it is preferred that all of Ar ¹ have a hydroxyl group. Further, Ar ^{1 is} preferably a hydroxyphenyl group which may have a substituent, and more preferably a hydroxyphenyl group having one or more aliphatic hydrocarbon groups having 1 to 6 carbon atoms.

R ¹ in the above structural formula (1) is a hydrogen atom or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be either a linear one or a branched structure, or may be one having an unsaturated group in the structure and no unsaturated group in the structure. The number of carbon atoms is not particularly limited, and may be any one of a short chain having 1 to 6 carbon atoms or a relatively long chain having 7 or more carbon atoms. Among them, R ^{1 is} preferably a hydrogen atom in terms of a phenolic hydroxyl group-containing resin which is more excellent in fluidity or heat resistance.

The R ² in the above structural formula (1) may have any one of an aliphatic hydrocarbon group, an alkoxy group and a halogen atom which may have a substituent. The aliphatic hydrocarbon group may be either a linear one or a branched structure, or may be one having an unsaturated group in the structure and no unsaturated group in the structure. The number of carbon atoms is not particularly limited, and may be any one of a short chain having 1 to 6 carbon atoms or a relatively long chain having 7 or more carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and a cyclohexyloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Among them, n is preferably 0 in terms of a phenolic hydroxyl group-containing resin which is more excellent in fluidity or heat resistance.

According to the above, the compound (A) is particularly preferably a compound represented by the following structural formula (1-1).

[In the formula, R ³ is an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and m is an integer of 1 to 4]

The above compound (A) can be produced by any method, and the production method is not particularly limited. As an example of the method for producing the above compound (A), for example, a method in which a phenol compound (a1) and a dimethyl hydrazine aromatic hydrocarbon compound (a2) are subjected to a condensation reaction can be mentioned.

The phenol compound (a1) may, for example, be a compound in which one or more hydrogen atoms on the aromatic nucleus of phenol or phenol are substituted with an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, a halogen atom or the like. These may be used alone or in combination of two or more. Among them, the phenolic hydroxyl group-containing resin which is excellent in heat resistance or dry etching resistance is preferably a phenol compound having one or more aliphatic hydrocarbon groups having 1 to 6 carbon atoms, more preferably 2 A phenolic compound of an aliphatic hydrocarbon group having 1 to 6 carbon atoms. At this time, the substitution position of the two aliphatic hydrocarbon groups is preferably the 2, 5- or 2, 6-position of the phenolic hydroxyl group.

The above-mentioned dimethyl fluorene-containing aromatic hydrocarbon compound (a2) is not particularly limited as long as it is an aromatic compound having two fluorenyl groups, and any compound can be used. Further, the substitution position on the aromatic nucleus of the two carbenyl groups is not particularly limited. Specific examples of the dimethyl fluorene-based aromatic hydrocarbon compound (a2) include dimethyl hydrazine benzene, dimethyl decyl naphthalene, dimethyl hydrazine hydrazine, and one or more hydrogen atoms on the aromatic rings. A compound substituted with an alkyl group, an alkoxy group, a halogen atom or the like. The dimethylidene aroma compound (a2) may be used alone or in combination of two or more. Among them, in the case of a phenolic hydroxyl group-containing resin which is excellent in balance between fluidity, heat resistance and dry etching resistance, it is preferably dimethyl phenylbenzene and one or more hydrogen atoms thereof on the aromatic ring thereof. A compound substituted with an alkyl group, an alkoxy group, a halogen atom or the like is more preferably dimethyl phenylbenzene.

The target compound (A) can be obtained in high yield and high purity, and the molar ratio [(a1)/(a2)] of the phenol compound (a1) to the dimethyl hydrazine compound (a2) is preferably Range of 1/0.1~1/0.5.

The reaction of the phenol compound (a1) with the dimethyl hydrazine aromatic compound (a2) is preferably carried out under acid catalyst conditions. Examples of the acid catalyst used herein include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts may be used alone or in combination of two or more. Among these, sulfuric acid and p-toluenesulfonic acid are preferred in terms of excellent catalyst activity.

The reaction of the phenol compound (a1) with the dimethyl hydrazine aromatic compound (a2) can be carried out in an organic solvent as needed. Examples of the solvent to be used herein include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentane. Alcohol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, Polyols such as glycerin; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol II a glycol ether such as methyl ether, ethylene glycol ethyl methyl ether or ethylene glycol monophenyl ether; Alkane, 1,4-two a cyclic ether such as an alkane, tetrahydrofuran or cyclopentyl methyl ether; a glycol ester such as ethylene glycol acetate; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone. These solvents may be used singly or in combination of two or more kinds.

The reaction of the phenol compound (a1) with the dimethyl hydrazine aromatic compound (a2) is carried out, for example, at a temperature of from 60 to 140 ° C for 0.5 to 20 hours.

After completion of the reaction, the reaction product is purified by washing with water or by reprecipitation, whereby a compound (A) of higher purity can be obtained. The fineness of the compound (A) is not particularly limited, and it is calculated based on the area ratio of the GPC line graph in terms of further improving the fluidity, heat resistance, developability, or dry etching resistance of the phenolic hydroxyl group-containing resin. The value is preferably 90% or more, more preferably 95% or more.

In the present invention, the purity of the compound (A) is a value calculated from the area ratio of the line graph obtained by GPC measurement under the following conditions. Further, the molecular weight or polydispersity index (Mw/Mn) of the following resin is a value measured by GPC measurement under the following conditions.

 [Measurement conditions of GPC]  

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Co., Ltd.

Pipe column: "Shodex KF802" (8.0mm Φ × 300mm) manufactured by Showa Denko Co., Ltd. + "Shodex KF802" (8.0mm Φ × 300mm) manufactured by Showa Denko Co., Ltd. + "Shodex KF803" manufactured by Showa Denko Co., Ltd. (8.0mmΦ×300mm) + "Shodex KF804" (8.0mmΦ×300mm) manufactured by Showa Denko Co., Ltd.

Column temperature: 40 ° C

Detector: RI (differential refractometer)

Data Processing: "GPC-8020 Model II Version 4.30" manufactured by Tosoh Co., Ltd.

Developing solvent: tetrahydrofuran

Flow rate: 1.0 mL/min

Sample: Filtered by a microfilter to a solution of 0.5% by mass of a resin solid content in tetrahydrofuran (100 μl)

Standard sample: monodisperse polystyrene described below

(Standard sample: monodisperse polystyrene)

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

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

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

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

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

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

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

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

In the case of producing the phenolic hydroxyl group-containing resin of the present invention, as the compound (A), a single structure may be used alone, or a plurality of compounds having different structures may be used in combination. Further, a phenolic hydroxyl group-containing compound (A') other than the above compound (A) may be used in combination. Examples of the other phenolic hydroxyl group-containing compound (A') include phenol, cresol, xylenol, phenylphenol, dihydroxybenzene, biphenol, bisphenol, naphthol, and dihydroxynaphthalene. These may be used alone or in combination of two or more. When the other phenolic hydroxyl group-containing compound (A') is used, the total amount of the compound (A) and the other phenolic hydroxyl group-containing compound (A') is 100 mass in terms of the effects of the present invention. In the above, the compound (A) is preferably used in a ratio of 70 parts by mass or more, and more preferably used in a ratio of 90 parts by mass or more.

The aldehyde compound (B) may be a condensation reaction with the compound (A). For example, in addition to formaldehyde, an aliphatic aldehyde compound such as acetaldehyde or propionaldehyde; benzaldehyde or hydroxybenzaldehyde may be mentioned. An aromatic aldehyde compound such as naphthaldehyde or hydroxynaphthaldehyde. These may be used alone or in combination of two or more. Among them, in terms of excellent reactivity, it is preferred to use formaldehyde or an aromatic aldehyde compound. The formaldehyde may be used in the form of a formalin in the form of an aqueous solution, or may be used in the form of a paraformaldehyde in a solid state, and may be either. When the above-mentioned formaldehyde and aromatic aldehyde compound are used in combination, it is preferred to use an aromatic aldehyde compound in the range of 0.5 to 5 moles per mole of formaldehyde.

The reaction method of the above compound (A) and the above aldehyde compound (B) is not particularly limited, and for example, it can be reacted in the same manner as in the production method of a general novolak resin.

The reaction molar ratio [(A)/(B)] of the compound (A) and the aldehyde compound (B) is appropriately adjusted according to the desired molecular weight or the like, so that excessive polymerization can be suppressed, and an anti-antioxidation can be obtained. The phenolic hydroxyl group-containing resin having an appropriate molecular weight of the etchant material preferably ranges from 1/0.5 to 1/3, more preferably from 1/0.8 to 1/2.

When the above-mentioned other phenolic hydroxyl group-containing compound (A') is used in combination, the molar ratio of the total (P) of the phenolic hydroxyl group-containing compound raw materials to the aldehyde compound (B) [(P)/(B)] It is preferably in the range of 1/0.5 to 1/3, more preferably in the range of 1/0.8 to 1/2.

The reaction of the above compound (A) with the above aldehyde compound (B) is preferably carried out under acid catalyst conditions. Examples of the acid catalyst used herein include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts may be used alone or in combination of two or more. Among these, sulfuric acid and p-toluenesulfonic acid are preferred in terms of excellent catalyst activity.

The reaction of the above compound (A) with the above aldehyde compound (B) can be carried out in an organic solvent as needed. Examples of the solvent to be used herein include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol. 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin Polyol; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol a glycol ether such as ether, ethylene glycol ethyl methyl ether or ethylene glycol monophenyl ether; Alkane, 1,4-two a cyclic ether such as an alkane, tetrahydrofuran or cyclopentyl methyl ether; a glycol ester such as ethylene glycol acetate; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone. These solvents may be used singly or in combination of two or more kinds.

The reaction of the above compound (A) with the above aldehyde compound (B) is carried out, for example, at a temperature of from 60 to 140 ° C for 0.5 to 20 hours.

After completion of the reaction, the reaction product can be purified by washing with water or reprecipitation to obtain a resin having a target phenolic hydroxyl group.

The phenolic hydroxyl group-containing resin of the present invention preferably has a weight average molecular weight (Mw) of from 3,000 to 50,000 in terms of a phenolic hydroxyl group-containing resin having excellent balance of fluidity, heat resistance and dry etching resistance. More preferably, it is in the range of 3,000 to 10,000. Further, the polydispersity index (Mw/Mn) of the phenolic hydroxyl group-containing resin is preferably in the range of 1.1 to 10.0, more preferably in the range of 1.1 to 5.0, and particularly preferably in the range of 1.5 to 3.5.

The phenolic hydroxyl group-containing resin of the present invention described in detail above can be used for various applications such as a coating material, an adhesive, an electric or electronic member, a photoresist, and a liquid crystal alignment film, similarly to a general phenol resin. Among them, as a material which is effective in utilizing characteristics of high fluidity, heat resistance, developability, or dry etching resistance, it is particularly suitable for a resist material, and can be used for a resist underlayer film in addition to a general interlayer insulating film. Various resist members such as a resist permanent film.

The photosensitive composition of the present invention contains the phenolic hydroxyl group-containing resin of the present invention and a sensitizer as essential components. The sensitizer may, for example, be a compound having a quinonediazide group. Specific examples of the compound having a quinonediazide group include an aromatic (poly) hydroxy compound and a quinonediazide group such as 1,2-naphthoquinone-2-diazide-5-sulfonic acid. A complete ester compound, a partial ester compound, a amide or a partial amide of a sulfonic acid or a halide thereof.

Examples of the above aromatic (poly)hydroxyl compound include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, and 2,4,6-trihydroxybenzophenone. Ketone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4',6-pentahydroxybenzophenone, 2,2',3,4,4'-pentahydroxy Benzophenone, 2,2',3,4,5-pentahydroxybenzophenone, 2,3',4,4',5',6-hexahydroxybenzophenone, 2,3,3 Polyhydroxybenzophenone compounds such as ',4,4',5'-hexahydroxybenzophenone; bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl) Methane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxybenzene Propane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 4,4'-[1-[4-[ 1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol, 3,3'-dimethyl-{1-[4-[2-(3-methyl) Bis[(poly)hydroxyphenyl]alkane compounds such as 4-hydroxyphenyl)-2-propyl]phenyl]ethylidene}bisphenol; quinone (4-hydroxyphenyl)methane, bis(4-hydroxyl) -3,5-dimethylphenyl)-4-hydroxyl Phenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenyl Methane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxybenzene Methane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, etc. (hydroxyphenyl)methane compound or methyl substitute thereof; bis (3-ring) Hexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl) 4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylbenzene 3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)- 3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl) -3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxybenzene) 4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)- Bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methane compound such as 2-hydroxyphenylmethane or bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane or Methyl substitutions, etc. These sensitizers may be used alone or in combination of two or more.

In the photosensitive composition having excellent photosensitivity, the amount of the photosensitive agent to be added in the photosensitive composition of the present invention is preferably 5 parts by mass based on 100 parts by mass of the total of the resin solid content of the photosensitive composition. ~50 parts by mass ratio.

In the photosensitive composition of the present invention, in addition to the above-mentioned phenolic hydroxyl group-containing resin of the present invention, other resin (X) may be used in combination. Examples of the other resin (X) used herein include, for example, various novolac resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, compounds containing phenolic hydroxyl groups, and alkoxy groups. Modified aromatic phenolic resin, phenol aralkyl resin (ZYLOCK resin), naphthol aralkyl resin, trimethylolethane resin, tetraphenylolethane resin, biphenyl modification Phenolic resin, biphenyl modified naphthol resin, amine base Modification of phenol resin, various vinyl polymers, and the like.

More specifically, the above various novolak resins may be exemplified by a polymer obtained by using an alkylphenol such as phenol, cresol or xylenol, phenylphenol, resorcin, biphenyl, bisphenol A or A phenolic hydroxyl group-containing compound such as bisphenol F, naphthol or dihydroxynaphthalene is reacted with an aldehyde compound under acid catalyst conditions.

Examples of the above various vinyl polymers include polyhydroxystyrene, polystyrene, polyvinyl naphthalene, polyvinyl anthracene, polyvinylcarbazole, polyfluorene, polyfluorene, polydecene, polycyclononene, A homopolymer of a vinyl compound such as polytetracyclododecene, polynortricyclene or poly(meth)acrylate or a copolymer of the same.

When the other resin is used, the blend ratio of the phenolic hydroxyl group-containing resin of the present invention to the other resin (X) can be arbitrarily set according to the use, and the effect exerted by the present invention can be more remarkably exhibited. In other words, it is preferable that the other resin (X) is in a ratio of 0.5 to 100 parts by mass based on 100 parts by mass of the phenolic hydroxyl group-containing resin of the present invention.

In addition, in the case where the phenolic hydroxyl group-containing resin of the present invention is excellent in light sensitivity, when it is used as a sensitivity enhancer, it is preferably contained in 100 parts by mass of the other resin (X). The phenolic hydroxyl group resin is in the range of 3 to 80 parts by mass.

The photosensitive composition of the present invention may contain a surfactant based on the purpose of improving film formability or pattern adhesion when used in the case of a resist. The surfactant used herein may, for example, be a polyoxyethylene alkyl ether compound such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether or polyoxyethylene oleyl ether, or polyoxyethylene octyl group. Polyoxyethylene alkyl allyl ether compound such as phenol ether or polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymer, sorbitan monolaurate, sorbitan monopalmitate, Yamanashi Sorbitan fatty acid ester compound such as alcohol anhydride monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate Polyoxyl such as ester, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate a nonionic surfactant such as an ethylene sorbitan fatty acid ester compound; a copolymer having a fluoroaliphatic group and a copolymer of [poly(oxyalkyl)] (meth) acrylate; Fluorine-based surfactant of atom; polyfluorene structure in molecular structure Bit of polyethylene oxide silicon-based surfactant and the like. These may be used alone or in combination of two or more.

The blending amount of the surfactant is preferably in the range of 0.001 to 2 parts by mass based on 100 parts by mass of the total of the resin solid content in the photosensitive composition of the present invention.

When the photosensitive composition of the present invention is used for a resist application, in addition to the phenolic hydroxyl group-containing resin or the sensitizer of the present invention, other resin (X) or a surfactant may be further added as needed. Various additives such as a dye, a filler, a crosslinking agent, and a dissolution promoter are dissolved in an organic solvent, whereby a photosensitive resist material is obtained. The photosensitive resist material can be used as a coating material as it is, and a photosensitive resist material can be applied to a support film and desolventized as a resist film. The support film used as the resist film may, for example, be a synthetic resin film such as polyethylene, polypropylene, polycarbonate or polyethylene terephthalate, and may be a single layer film or a multilayer laminated film. Further, the surface of the support film may be a corona treatment or a release agent.

The type of the organic solvent is not particularly limited, and examples thereof include an alkylene such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether. a diol monoalkyl ether; a diene glycol dialkyl ether such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether or diethylene glycol dibutyl ether; Alkenyl glycol alkyl ether acetate such as diol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; acetone, methyl ethyl ketone, cyclohexanone, a ketone compound such as pentyl ketone; Alkane and other cyclic ether; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl oxyacetate, 2- Methyl hydroxy-3-methylbutanoate, butyl 3-methoxyacetate, butyl 3-methyl-3-methoxyacetate, ethyl formate, ethyl acetate, butyl acetate, ethyl acetate An ester compound such as an ester or ethyl acetate may be used alone or in combination of two or more.

The photosensitive resist material can be produced by blending the above components and mixing them using a stirrer or the like. Further, when the resist material contains a filler or a pigment, it may be produced by dispersing or mixing using a dispersing device such as a dispersing mixer, a homogenizer or a three-roll mill.

As a method of using the general photolithography of the above-mentioned photosensitive resist material, for example, the method described below can be mentioned. First, the photosensitive resist material is applied onto a target of photolithography such as a tantalum substrate, a tantalum carbide substrate, or a gallium nitride substrate, and prebaked at a temperature of 60 to 150 °C. The coating method at this time may be any one of spin coating, roll coating, flow coating, dip coating, spray coating, blade coating, and the like. Then, exposure is performed by a resist pattern, and development is performed by an alkaline developing solution, thereby forming a resist pattern.

When the photosensitive resist material is used for a resist permanent film application, it is preferred to contain a crosslinking agent together with the photosensitive agent. The crosslinking agent used herein may be the same as the curing agent used in the following curable composition. A method of forming a resist permanent film can be exemplified by the method described below. First, the photosensitive resist material is applied onto a target of photolithography such as a tantalum substrate, a tantalum carbide substrate, or a gallium nitride substrate, and prebaked at a temperature of 60 to 150 °C. The coating method is the same as that enumerated previously. Then, it is exposed by a resist pattern, further thermally cured at a temperature of 110 to 210 ° C, and then developed by an alkaline developing solution to form a resist pattern. Alternatively, after exposure, development may be carried out by an alkaline developing solution, followed by thermal hardening at a temperature of 110 to 210 °C.

Specific examples of the resist permanent film include a solder resist, a potting material, an underfill material, a package via layer of a circuit element, an integrated circuit element, and an underlayer of a circuit board. Further, examples of the thin display represented by LCD and OELD include a thin film transistor protective film, a liquid crystal color filter protective film, a black matrix, and a spacer.

The curable composition of the present invention contains the phenolic hydroxyl group-containing resin of the present invention and a curing agent as essential components. Further, in addition to the above phenolic hydroxyl group-containing resin of the present invention, other resins (Y) may be used in combination. Examples of the other resin (Y) used herein include, for example, various novolac resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, compounds containing phenolic hydroxyl groups, and alkoxy groups. Aromatic compound modified novolac resin, phenol aralkyl resin (ZYLOCK resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenol ethane resin, biphenyl modified phenol resin, biphenyl Modified naphthol resin, amine base three Modified phenolic resin, and various vinyl polymers.

More specifically, the above various novolak resins may be exemplified by a polymer obtained by using an alkylphenol such as phenol, cresol or xylenol, phenylphenol, resorcin, biphenyl, bisphenol A or A phenolic hydroxyl group-containing compound such as bisphenol F, naphthol or dihydroxynaphthalene is reacted with an aldehyde compound under acid catalyst conditions.

Examples of the above various vinyl polymers include polyhydroxystyrene, polystyrene, polyvinyl naphthalene, polyvinyl anthracene, polyvinylcarbazole, polyfluorene, polyfluorene, polydecene, polycyclononene, A homopolymer of a vinyl compound such as polytetracyclododecene, polynortrienol or poly(meth)acrylate or a copolymer of the same.

When the other resin is used, the blend ratio of the phenolic hydroxyl group-containing resin of the present invention to the other resin (Y) can be arbitrarily set according to the use, and the effect of the present invention can be more remarkably exhibited. It is preferable that the other resin (Y) is a ratio of 0.5 to 100 parts by mass based on 100 parts by mass of the phenolic hydroxyl group-containing resin of the present invention.

The curing agent used in the present invention is not particularly limited as long as it is a compound which can undergo a curing reaction with the phenolic hydroxyl group-containing resin of the present invention, and various compounds can be used. Moreover, the curing method of the curable composition of the present invention is not particularly limited, and it can be cured by an appropriate method such as thermal curing or photocuring depending on the type of the curing agent or the type of the curing accelerator described below. The curing temperature such as the heating temperature or time in the thermal curing, the type of light in the photocuring, or the exposure time can be appropriately adjusted depending on the type of the curing agent or the type of the curing accelerator described below.

Specific examples of the curing agent include a melamine compound, a guanamine compound, an acetylene urea compound, a urea compound, a resol resin, an epoxy compound, an isocyanate compound, an azide compound, and a double bond including an alkenyl ether group. Compound, acid anhydride, An oxazoline compound or the like.

Examples of the melamine compound include a compound obtained by methoxymethylating hexamethylenemethyl melamine, hexamethoxymethyl melamine, and hexamethylol melamine with 1 to 6 methylol groups, and hexamethoxyethyl group. A compound obtained by subjecting melamine methylation to melamine, hexamethoxymethyl melamine or hexamethylol melamine from 1 to 6 methylol groups.

Examples of the above guanamine compound include 1,4-hydroxymethyl decylamine, tetramethoxymethyl decylamine, tetramethoxymethyl benzoguanamine, and tetrahydroxymethyl decylamine in 1 to 4 hydroxymethyl groups. a methoxymethylated product of a methoxymethylated compound, tetramethoxyethylguanamine, tetradecyloxyguanamine, and tetrahydroxymethylguanamine Compounds and the like.

Examples of the above acetylene urea compound include 1,3,4,6-fluorene (methoxymethyl)acetylene urea, 1,3,4,6-fluorene (butoxymethyl)acetylene urea, 1,3. 4,6-fluorene (hydroxymethyl) acetylene urea and the like.

Examples of the urea compound include 1,3-bis(hydroxymethyl)urea, 1,1,3,3-indenyl (butoxymethyl)urea, and 1,1,3,3-anthracene (methoxyl). Methyl)urea and the like.

Examples of the resole phenol resin include a polymer obtained by using an alkylphenol such as phenol, cresol or xylenol, phenylphenol, resorcin, biphenyl, bisphenol A or bisphenol F. A phenolic hydroxyl group-containing compound such as bisphenol, naphthol or dihydroxynaphthalene is reacted with an aldehyde compound under a basic catalyst condition.

Examples of the epoxy compound include diepoxypropoxy naphthalene, phenol novolak epoxy resin, cresol novolak epoxy resin, naphthol novolac epoxy resin, and naphthol-phenol copolyphenol novolak. Epoxy resin, naphthol-cresol copolyphenolic epoxidized epoxy resin, phenol aralkyl epoxy resin, naphthol aralkyl epoxy resin, 1,1-bis (2,7-bicyclo) Oxypropoxy-1-naphthyl)alkane, stretch naphthyl ether type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phosphorus atom containing epoxy A polyglycidyl ether of a resin, a phenolic hydroxyl group-containing compound, and a cocondensate containing an alkoxy aromatic compound.

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

Examples of the above azide compound include 1,1'-biphenyl-4,4'-diazide, 4,4'-methylidene diazide, 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-propylene glycol divinyl ether, and 1,4-butanediol divinyl ether. Tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, neopentyl alcohol Trivinyl ether, neopentyl alcohol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, and the like.

Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, and biphenyltetracarboxylic dianhydride. , 4,4'-(isopropylidene)diphthalic anhydride, aromatic anhydride such as 4,4'-(hexafluoroisopropylidene)diphthalic anhydride; tetrahydrophthalic anhydride , methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, three An alicyclic carboxylic acid anhydride such as an alkyltetrahydrophthalic anhydride.

Among these, the curable composition which is excellent in heat resistance in the curable or cured product is preferably an acetylene urea compound, a urea compound or a resol resin, and particularly preferably an acetylene urea compound.

The blending amount of the above-mentioned hardener in the curable composition of the present invention is preferably 100 in total with respect to the phenolic hydroxyl group-containing resin of the present invention and the other resin (X). The mass fraction is a ratio of 0.5 to 50 parts by mass.

The curable composition of the present invention may contain a hardening accelerator together with the above-mentioned curing agent. In the case where the curable composition of the present invention is thermally cured, an acid compound such as acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate or manganese acetate is preferably used as the curing accelerator. On the other hand, in the case where the curable composition of the present invention is photocured, it is preferred to use a photoacid generator as a curing accelerator. The photoacid generator may, for example, be a sulfonium salt compound such as gin(4-methylphenyl)phosphonium trifluoromethanesulfonate or ginseng (4-methylphenyl)phosphonium hexafluorophosphate; bis(4-n-hexane) Phenyl hexafluorophosphate, bis(4-n-alkylphenyl)phosphonium hexafluoroantimonate, bis(4-t-butylphenyl)phosphonium hexafluorophosphate, double (4-third A sulfonium salt compound such as butylphenyl) bis(perfluorobutylsulfonyl) fluorene and bis(4-n-alkylphenyl)phosphonium (pentafluorophenyl)borate (n-hexane in each compound) The base is preferably a carbon number of 10 to 13); 2-[2-(furan-2-yl)ethynyl]-4,6-bis(trichloromethyl) symmetric three 2-[2-(methylfuran-2-yl)ethynyl]-4,6-bis(trichloromethyl)symmetric three 2-(methoxyphenyl)-4,6-bis(trichloromethyl)symmetric three 2-[2-(4-methoxyphenyl)ethynyl]-4,6-bis(trichloromethyl)symmetric three 2-[2-(3,4-Dimethoxyphenyl)ethynyl]-4,6-bis(trichloromethyl)symmetric three Chloromethyl three Compounds, etc. The hardening accelerators may be used alone or in combination of two or more. The amount of the hardening accelerator added is preferably in the range of 0.1 to 10% by mass based on the resin solid content of the curable composition.

When the curable composition of the present invention is used for a resist application, in addition to the phenolic hydroxyl group-containing resin and the hardener of the present invention, other resins (Y), surfactants or other additives may be added as needed. Various additives such as a dye, a filler, a crosslinking agent, and a dissolution promoter are dissolved in an organic solvent, whereby a curable resist material can be obtained. The curable resist material can be used as a coating material as it is, or a resist film can be applied by applying a curable resist material to a support film and performing solvent removal. The support film used as the resist film may, for example, be a synthetic resin film such as polyethylene, polypropylene, polycarbonate or polyethylene terephthalate, and may be a single layer film or a multilayer laminated film. Further, the surface of the support film may be a corona treatment or a release agent.

The type of the organic solvent is not particularly limited, and examples thereof include an alkenyl glycol such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether. Monoalkyl ether; diethylene glycol dialkyl ether such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; ethylene glycol single Alkenyl glycol alkyl ether acetate such as methyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; acetone, methyl ethyl ketone, cyclohexanone, methyl amyl Ketone and other ketone compounds; Alkane and other cyclic ether; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl oxyacetate, 2- Methyl hydroxy-3-methylbutanoate, butyl 3-methoxyacetate, butyl 3-methyl-3-methoxyacetate, ethyl formate, ethyl acetate, butyl acetate, ethyl acetate An ester compound such as an ester or ethyl acetate may be used alone or in combination of two or more.

The curable resist material can be produced by blending the above components and mixing them using a stirrer or the like. Further, when the resist material contains a filler or a pigment, it may be produced by dispersing or mixing using a dispersing device such as a dispersing mixer, a homogenizer or a three-roll mill.

When the above-mentioned curable resist material is used for the use of a resist underlayer film, as an example of a method of forming a resist underlayer film, for example, a resist underlayer film is formed by the following method: The resist material is applied to a target for photolithography such as a tantalum substrate, a tantalum carbide substrate, or a gallium nitride substrate, and dried at a temperature of 100 to 200 ° C, and further at a temperature of 250 to 400 ° C. Heat hardening is carried out. Then, a normal light lithography operation is performed on the underlying film to form a resist pattern, and a dry etching process is performed by a halogen-based plasma gas or the like, whereby a resist pattern using a multilayer resist method can be formed. .

 [Examples]  

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

In the examples of the present invention, the purity of the compound (A) is a value calculated from the area ratio of the line graph obtained by GPC measurement under the following conditions. Further, the number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity index (Mw/Mn) of the synthesized resin were measured under the measurement conditions of GPC described below.

 [Measurement conditions of GPC]  

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Co., Ltd.

Pipe column: "Shodex KF802" (8.0mm Φ × 300mm) manufactured by Showa Denko Co., Ltd. + "Shodex KF802" (8.0mm Φ × 300mm) manufactured by Showa Denko Co., Ltd. + "Shodex KF803" manufactured by Showa Denko Co., Ltd. (8.0mmΦ×300mm) + "Shodex KF804" (8.0mmΦ×300mm) manufactured by Showa Denko Co., Ltd.

Column temperature: 40 ° C

Detector: RI (differential refractometer)

Data Processing: "GPC-8020 Model II Version 4.30" manufactured by Tosoh Co., Ltd.

Developing solvent: tetrahydrofuran

Flow rate: 1.0 mL/min

Sample: Filtered by a microfilter to filter a tetrahydrofuran solution having a resin solid content of 0.5% by mass

Injection volume: 0.1mL

Standard sample: monodisperse polystyrene described below

(Standard sample: monodisperse polystyrene)

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

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

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

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

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

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

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

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

The measurement of the ¹³ C-NMR spectrum was carried out under the following conditions.

Measuring device: "AL-400" manufactured by JEOL Ltd.

Solvent: DMSO-d ₆

Sample concentration: 30wt%

Measurement mode: SGNNE ( ¹ H complete decoupling method to eliminate NOE)

Pulse angle: 45 ° C pulse

Cumulative number: 10,000 times

Production Example 1 Production of Compound (A-1)

To a 100 ml two-necked flask equipped with a cooling tube, 73 g of 2,5-xylenol and 20 g of terephthalaldehyde were added, and these were dissolved in 300 ml of 2-ethoxyethanol. After adding 10 g of sulfuric acid while cooling in an ice bath, the reaction was carried out while stirring in an oil bath of 80 ° C for 2 hours. After the end of the reaction, water was added to the obtained reaction mixture to precipitate a crude product. The recovered crude product was dissolved in acetone, and water was again added to reprecipitate the product. The precipitate was separated by filtration and dried under vacuum to give 62 g of Compound (A-1) as a pale red powder. The purity of the compound (A-1) calculated based on the area ratio of the GPC line chart was 98.2%. The GPC of the compound (A-1) is shown in Fig. 1, and the ¹³ C-NMR chart is shown in Fig. 2.

Example 1 Production of Resin Containing Phenolic Hydroxyl Group (1)

To a four-necked flask of 100 ml in which a cooling tube was placed, 18.3 g of the above compound (A-1) and 4.6 g of salicylaldehyde were added, and these were dissolved in 54.9 g of 2-ethoxyethanol. After adding 2.8 g of 98 wt% sulfuric acid, the mixture was heated to 100 ° C and heated for 14 hours. After the reaction was completed, water was added to the reaction mixture to precipitate a crude product. The recovered crude product was dissolved in acetone, and water was again added to reprecipitate. The precipitate was separated by filtration and vacuum dried to obtain 20.3 g of a red powdery phenolic hydroxyl group-containing resin (1). The phenolic hydroxyl group-containing resin (1) had a number average molecular weight (Mn) of 1,354, a weight average molecular weight (Mw) of 5,270, and a polydispersity index (Mw/Mn) of 1.95. The GPC of the phenolic hydroxyl group-containing resin (1) is shown in Fig. 3.

Example 2 Production of Resin Containing Phenolic Hydroxyl Group (2)

To a four-necked flask of 100 ml in which a cooling tube was placed, 18.3 g of the above compound (A-1), 4.6 g of salicylaldehyde, and 0.4 g of 92% formaldehyde were added, and these were dissolved in 54.9 g of 2-ethoxyethanol. in. After adding 2.8 g of 98 wt% sulfuric acid, the mixture was heated to 100 ° C for 14 hours. After the reaction was completed, water was added to the reaction mixture to precipitate a crude product. The recovered crude product was dissolved in acetone, and water was again added to reprecipitate. The precipitate was separated by filtration and vacuum dried to obtain 20.5 g of a red powder of a phenolic hydroxyl group-containing resin (2). The phenolic hydroxyl group-containing resin (2) had a number average molecular weight (Mn) of 1,949, a weight average molecular weight (Mw) of 5,286, and a polydispersity index (Mw/Mn) of 2.71. The GPC chart of the phenolic hydroxyl group-containing resin (2) is shown in Fig. 4.

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

In a four-necked flask equipped with a stirrer and a thermometer, 648 g of m-cresol, 432 g of p-cresol, 2.5 g of oxalic acid, and 492 g of 42% formaldehyde were added, and the mixture was heated to 100 ° C to carry out a reaction. The mixture was heated to 200 ° C under normal pressure for dehydration and distillation, and further distilled under reduced pressure at 230 ° C for 6 hours to obtain 736 g of a phenolic hydroxyl group-containing resin (1') as a pale yellow solid. The phenolic hydroxyl group-containing resin (1') had a number average molecular weight (Mn) of 1,450, a weight average molecular weight (Mw) of 10,316, and a polydispersity index (Mw/Mn) of 7.12.

Examples 3 and 4 and Comparative Example 1

The phenolic hydroxyl group-containing resin obtained in Comparative Example 1 and Comparative Example 1 was evaluated in the following points. The results are shown in Table 1.

Manufacture of photosensitive composition

8 parts by mass of the phenolic hydroxyl group-containing resin was dissolved in 40 parts by mass of propylene glycol monomethyl ether acetate, and 2 parts by mass of a photosensitive agent was added to the solution and dissolved. This was filtered through a 0.2 μm membrane filter to obtain a photosensitive composition.

The sensitizer is "P-200" (4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl)phenyl] manufactured by Toyo Seiki Co., Ltd. Ethylene] bisphenol 1 molar and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride 2 molar condensate).

Manufacture of heat resistance test composition

8 parts by mass of the phenolic hydroxyl group-containing resin was dissolved in 40 parts by mass of propylene glycol monomethyl ether acetate, and the mixture was filtered through a 0.2 μm membrane filter to obtain a heat resistance test composition.

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

The previously obtained photosensitive composition was applied onto a 5 inch wafer by a spin coater so as to have a thickness of about 1 μm, and dried on a hot plate at 110 ° C for 60 seconds. Two wafers are prepared, and one is set to "no exposure sample". The other one is set to "exposed sample", and the ghi line lamp ("Multilight" manufactured by USHIO Electric Co., Ltd.) is used to irradiate the ghi line of 100 mJ/cm ² , and then heat-treated at 140 ° C for 60 seconds. .

Both the "non-exposed sample" and the "exposed sample" were immersed in an alkaline developing solution (2.38% aqueous solution of tetramethylammonium hydroxide) for 60 seconds, and then dried on a hot plate at 110 ° C for 60 seconds. The film thickness before and after the immersion of the developer solution of each sample was measured, and the value obtained by dividing the difference by 60 was made alkaline developability [ADR (nm/s)].

Evaluation of light sensitivity

The previously obtained photosensitive composition was applied onto a 5 inch wafer by a spin coater so as to have a thickness of about 1 μm, and dried on a hot plate at 110 ° C for 60 seconds. Ghi line lamp (manufactured by USHIO Electric Co., Ltd.) is used to close the mask corresponding to the "resist pattern with a line and gap of 1:1 and a line width of 1 to 10 μm for each 1 μm increase" on the wafer. Multilight") The ghi line was irradiated and heat-treated at 140 ° C for 60 seconds. Then, it was immersed in an alkaline developing solution (2.38% aqueous solution of tetramethylammonium hydroxide) for 60 seconds, and then dried on a hot plate at 110 ° C for 60 seconds.

The exposure amount (Eop exposure amount) having a line width of 3 μm was faithfully reproduced when the ghi line exposure amount was increased by 10 mJ/cm ² from 100 mJ/cm ² .

Evaluation of resolution

The previously obtained photosensitive composition was applied onto a 5 inch wafer by a spin coater so as to have a thickness of about 1 μm, and dried on a hot plate at 110 ° C for 60 seconds. A photomask was placed on the obtained wafer, and a ghi wire of 200 mJ/cm ^{2 was} irradiated with a ghi wire lamp ("Multilight" manufactured by USHIO Electric Co., Ltd.), and then heat-treated at 140 ° C for 60 seconds. Then, it was immersed in an alkaline developing solution (2.38% aqueous solution of tetramethylammonium hydroxide) for 60 seconds, and then dried on a hot plate at 110 ° C for 60 seconds. The state of the pattern was confirmed using a laser microscope ("VK-X200" manufactured by KEYENCE Co., Ltd.). When the line width of L/S = 1/1 was 5 μm, the resolution was set to A, and L/S = 1/. When the line width of 1 is 5 μm, the unsolvable person is set to B and evaluated.

Heat resistance evaluation

The previously obtained heat resistance test composition was applied onto a 5 inch wafer by a spin coater so as to have a thickness of about 1 μm, and dried on a hot plate at 110 ° C for 60 seconds. The resin composition was scraped off from the obtained wafer, and the glass transition temperature (Tg) thereof was measured. The glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC) ("Q100" manufactured by TA Instruments, Inc.) under a nitrogen atmosphere at a temperature range of -100 to 250 ° C and a temperature rise temperature of 10 ° C / min. Under the conditions.

Examples 5, 6 and Comparative Example 2

The phenolic hydroxyl group-containing resin obtained in Comparative Example 1 and Comparative Example 1 was evaluated in the following points. The results are shown in Table 2.

Manufacture of hardenable composition

4 parts by mass of the phenolic hydroxyl group-containing resin and 1 part by mass of the curing agent were dissolved in 25 parts by mass of propylene glycol monomethyl ether acetate, and the mixture was filtered through a 0.2 μm membrane filter to obtain a curable composition.

The hardener was "1,3,4,6-fluorene (methoxymethyl) acetylene urea" manufactured by Tokyo Chemical Industry Co., Ltd.

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

The previously obtained curable composition was applied onto a 5 inch wafer by a spin coater at a thickness of about 1 μm, and dried on a hot plate at 110 ° C for 60 seconds. This was immersed in an alkaline developing solution (2.38% aqueous solution of tetramethylammonium hydroxide) for 60 seconds, and then dried on a hot plate at 110 ° C for 60 seconds. The film thickness before and after the immersion of the developer was measured, and the value obtained by dividing the difference by 60 was made alkaline developability [ADR (nm/s)].

Evaluation of dry etching resistance

The previously obtained hardenable composition was applied onto a 5 inch wafer by a spin coater, and dried on a hot plate at 180 ° C for 60 seconds in an environment of an oxygen concentration of 20% by volume. Then, it was heat-hardened at 350 ° C for 120 seconds to form a cured coating film having a film thickness of 0.3 μm. For the hardened coating film on the wafer, an etching apparatus ("EXAM" manufactured by Kobelco Seiki Co., Ltd.) was used in CF ₄ /Ar/O ₂ (CF ₄ : 40 mL / min, Ar: 20 mL / min, O ₂ : 5 mL / The etching treatment was carried out under the conditions of minute, pressure: 20 Pa, RF power: 200 W, treatment time: 40 seconds, and temperature: 15 ° C. The film thickness before and after the etching treatment at this time was measured, the etching rate was calculated, and the etching resistance was evaluated. The evaluation criteria are as follows.

A: The etching rate is 150 nm/min or less.

B: The etching rate exceeds 150 nm/min.

Liquidity evaluation

On a 5 inch diameter wafer having a hole pattern of Φ110 nm and a depth of 300 nm, the curable composition obtained before coating by a spin coater was exposed to an oxygen concentration of 20% by volume at 110 ° C. After drying on a hot plate for 180 seconds, it was heat-hardened at 210 ° C for 60 seconds to obtain a cured coating film having a film thickness of 0.3 μm. The tantalum wafer was cut on the hole pattern line, and the cross section was observed by a laser microscope ("VK-X200" manufactured by Keyence Co., Ltd.), and the hole pattern of the hardenable composition was evaluated under the following conditions. Is the inflow sufficient?

A: The hole is filled with hardened material as a whole.

B: The whole hole is not filled with hardened material, and there is a gap.

Claims (7)

A phenolic hydroxyl group-containing resin which is a reactant of the compound (A) represented by the following structural formula (1) and an aldehyde compound (B), Wherein Ar ^{1 is} each independently an aryl group which may have a substituent, at least one of Ar ¹ has a hydroxyl group on the aromatic ring; R ¹ is a hydrogen atom or an aliphatic hydrocarbon group; and R ² may have a substituent Any of an aliphatic hydrocarbon group, an alkoxy group, and a halogen atom, n is 0 or an integer of 1 to 4]. The phenolic hydroxyl group-containing resin according to the first aspect of the invention, wherein the compound (A) is a compound represented by the following structural formula (1-1). [In the formula, R ³ is an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and m is an integer of 1 to 4].  For example, the phenolic hydroxyl group-containing resin of the first application of the patent scope has a polydispersity index (Mw/Mn) ranging from 1.1 to 10.0.    A photosensitive composition comprising a phenolic hydroxyl group-containing resin and a sensitizer according to any one of claims 1 to 3.    A curable composition containing a phenolic hydroxyl group-containing resin and a curing agent according to any one of claims 1 to 3.    A cured product which is a cured product of the curable composition of claim 5 of the patent application.    A resist material using the phenolic hydroxyl group-containing resin according to any one of claims 1 to 3.