WO2018101058A1

WO2018101058A1 - Phenolic hydroxy group-containing resin and resist material

Info

Publication number: WO2018101058A1
Application number: PCT/JP2017/041224
Authority: WO
Inventors: 今田　知之; 勇介佐藤
Original assignee: Dic株式会社
Priority date: 2016-12-01
Filing date: 2017-11-16
Publication date: 2018-06-07
Also published as: TW201829513A; JP6590084B2; JPWO2018101058A1

Abstract

Provided are: a phenolic hydroxy group-containing resin having high fluidity and heat resistance, and having superior developability and dry etching resistance when used as a resist material, and a photosensitive compound, a curable composition, and a resist material which contain the phenolic hydroxy group-containing resin. Specifically, provided are a phenolic hydroxy group-containing resin which is a reaction product of a tri(hydroxyaryl)alkane compound (A) and a diformyl arene compound (B), and a photosensitive compound, a curable composition, and a resist material which use the phenolic hydroxy group-containing resin. The tri(hydroxyaryl)alkane compound (A) is preferably represented by structural formula (1-1) or (1-2) [in the formulas, R¹ and R² each independently represent any of an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, and a halogen atom, each l independently represents an integer of 0 or 1-4, m represents an integer of 0 or 1-4, n represents an integer of 0 or 1-6, and R³ represents a hydrogen atom or an alkyl group.].

Description

Phenolic hydroxyl group-containing resin and resist material

The present invention is a phenolic hydroxyl group-containing resin having high fluidity and heat resistance, and excellent in developability and dry etching resistance when used as a resist material, a photosensitive composition containing the same, a curable composition, and The present invention relates to a resist material.

In the field of photoresists, a variety of resist pattern forming methods that have been subdivided according to applications and functions have been developed one after another, and accordingly, the required performance for resist resin materials has become sophisticated and diversified. For example, a resin material for forming a pattern requires high developability for forming a fine pattern accurately and with high production efficiency on a highly integrated semiconductor. In applications called underlayer films, antireflection films, BARC films, hard masks, etc., dry etching resistance, low reflectivity, and high fluidity that can be applied to uneven substrate surfaces are required. In addition, in applications such as resist permanent films, toughness such as substrate followability is required in addition to high heat resistance. Furthermore, from the viewpoint of quality and reliability, long-term storage stability in various environments around the world is one of the important performances.

The phenolic hydroxyl group-containing resin most widely used for photoresist applications is of the cresol novolac type, but it is not capable of meeting the performance requirements of today's increasingly sophisticated and diversified, heat resistance, fluidity, Further improvements in various properties such as developability and dry etching resistance have been demanded (see Patent Document 1).

JP-A-2-55359

The problem to be solved by the present invention is a phenolic hydroxyl group-containing resin having high fluidity and heat resistance, and excellent in developability and dry etching resistance when used as a resist material, a photosensitive composition containing the same, The object is to provide a curable composition and a resist material.

As a result of intensive studies to solve the above problems, the present inventors have found that a phenolic hydroxyl group-containing resin, which is a reaction product of a tri (hydroxyaryl) alkane type compound and a diformylarene compound, has fluidity and heat resistance. As a result, the present invention has been completed by finding that it has high developability and excellent developability and dry etching resistance when used as a resist material.

That is, the present invention relates to a phenolic hydroxyl group-containing resin which is a reaction product of a tri (hydroxyaryl) alkane type compound (A) and a diformylarene compound (B).

The present invention further relates to a photosensitive composition containing the phenolic hydroxyl group-containing resin and a photosensitive agent.

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

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

The present invention further relates to a resist material using the phenolic hydroxyl group-containing resin.

According to the present invention, a phenolic hydroxyl group-containing resin having high fluidity and heat resistance and excellent developability and dry etching resistance when used as a resist material, a photosensitive composition containing the same, and a curable composition And resist materials can be provided.

FIG. 1 is a GPC chart of the tri (hydroxyaryl) alkane type compound (A-1) obtained in Production Example 1. FIG. 2 is a ¹³ C-NMR chart of the tri (hydroxyaryl) alkane type compound (A-1) obtained in Production Example 1. FIG. 3 is a GPC chart of the phenolic hydroxyl group-containing resin (1) obtained in Example 1. FIG. 4 is a GPC chart 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 a tri (hydroxyaryl) alkane type compound (A) and a diformylarene compound (B).

The tri (hydroxyaryl) alkane type compound (A) is an alkane compound having three aryl groups having a hydroxy group in its molecular structure, and its specific structure is not particularly limited. Especially, since it becomes phenolic hydroxyl-containing resin excellent in heat resistance especially, it is preferable that it is a compound which has all three hydroxyaryl groups on the same carbon atom. Specific examples of such a compound include, for example, the following structural formula (1-1) or (1-2)

[Wherein R ¹ and R ² are each independently an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group or a halogen atom. l is independently 0 or an integer of 1 to 4, m is an integer of 0 or 1 to 5, and n is an integer of 0 or 1 to 7. R ³ is a hydrogen atom or an alkyl group. ]
The compound represented by these is mentioned.

In the structural formulas (1-1) and (1-2), R ¹ is each independently an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, or a halogen atom, and l is each independently 0 or an integer of 1 to 4. The aliphatic hydrocarbon group may be either a straight chain type or a branched structure, and may have either an unsaturated group in the structure or not. The number of carbon atoms is not particularly limited, and may be a short chain having 1 to 6 carbon atoms or a relatively long chain having 7 or more carbon atoms. The specific structure of the aromatic ring-containing hydrocarbon group is not particularly limited as long as it is a structural part containing an aromatic ring. In addition to an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a benzyl group Aralkyl groups such as phenylethyl group, phenylpropyl group and naphthylmethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy 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, l is preferably an integer of 1 to 4, and more preferably 1 or 2, because the phenolic hydroxyl group-containing resin is excellent in heat resistance and dry etching resistance. R ¹ is preferably an aliphatic hydrocarbon group, more preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and any of a methyl group, an ethyl group, a propyl group, and a butyl group. It is particularly preferred.

R ² in the structural formulas (1-1) and (1-2) is each independently an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, or a halogen atom, and m is 0 or An integer of 1 to 5, n is 0 or an integer of 1 to 7. The aliphatic hydrocarbon group may be either a straight chain type or a branched structure, and may have either an unsaturated group in the structure or not. The number of carbon atoms is not particularly limited, and may be a short chain having 1 to 6 carbon atoms or a relatively long chain having 7 or more carbon atoms. The specific structure of the aromatic ring-containing hydrocarbon group is not particularly limited as long as it is a structural part containing an aromatic ring. In addition to an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a benzyl group Aralkyl groups such as phenylethyl group, phenylpropyl group and naphthylmethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy 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, R ² is preferably an aliphatic hydrocarbon group, and preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, because it becomes a phenolic hydroxyl group-containing resin having excellent heat resistance and dry etching resistance. Are more preferable, and any of a methyl group, an ethyl group, a propyl group, and a butyl group is particularly preferable. Moreover, m or n is preferably 0, 1, or 2, and more preferably 0.

R ³ in the structural formulas (1-1) and (1-2) is a hydrogen atom or an alkyl group, respectively. The alkyl group may be linear or may have a branched structure. The number of carbon atoms is not particularly limited, and may be a short chain having 1 to 6 carbon atoms or a relatively long chain having 7 or more carbon atoms. Among them, R ³ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, since it becomes a phenolic hydroxyl group-containing resin having an excellent balance of fluidity, heat resistance, and dry etching resistance. More preferably, it is any one of a methyl group, an ethyl group, a propyl group, and a butyl group.

The tri (hydroxyaryl) alkane type compound (A) can be produced, for example, by subjecting a phenol compound (a1) and a hydroxyl group-containing aromatic aldehyde compound (a2) to a condensation reaction, and Honshu Chemical Industry Co., Ltd. Commercially available products such as “TrisP-HAP” [1,1,1-tris (4-hydroxyphenyl) ethane] manufactured by the Company may be used. Hereinafter, an example of the manufacturing method in the case of manufacturing by making a phenol compound (a1) and an aromatic aldehyde compound (a2) carry out a condensation reaction is demonstrated.

In the phenol compound (a1), for example, one or more of hydrogen atoms on the aromatic nucleus of phenol or phenol is substituted with an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, a halogen atom, or the like. Compounds. These may be used alone or in combination of two or more. Among them, a phenol compound having an aliphatic hydrocarbon group having 1 to 6 carbon atoms is preferable because it becomes a phenolic hydroxyl group-containing resin having excellent heat resistance and dry etching resistance, and is preferably a methyl group, an ethyl group, a propyl group, or a butyl group. A phenol compound having any of the above is more preferred. The number of aliphatic hydrocarbon groups on the aromatic nucleus is preferably 1 to 4, and preferably 1 or 2. In particular, it is preferable to use 2,5-xylenol as the phenol compound (a1).

The hydroxyl group-containing aromatic aldehyde compound (a2) is, for example, hydroxybenzaldehyde, hydroxynaphthaldehyde, one or more of hydrogen atoms on the aromatic nucleus are aliphatic hydrocarbon groups, aromatic ring-containing hydrocarbon groups, Examples thereof include compounds substituted with an alkoxy group, a halogen atom or the like. Moreover, the substitution position of the formyl group and hydroxyl group on the aromatic nucleus is not particularly limited, and any compound may be used. The hydroxyl group-containing aromatic aldehyde compound (a2) may be used alone or in combination of two or more. Among them, hydroxybenzaldehyde or hydroxynaphthaldehyde is preferable because it becomes a phenolic hydroxyl group-containing resin having excellent heat resistance and dry etching resistance. Furthermore, hydroxybenzaldehyde is preferable and 4-hydroxybenzaldehyde is more preferable because it becomes a phenolic hydroxyl group-containing resin having excellent fluidity.

The reaction molar ratio [(a1) / (a2)] of the phenol compound (a1) and the hydroxyl group-containing aromatic aldehyde compound (a2) yields the target tri (hydroxyaryl) alkane type compound (A)) in a high yield. In addition, since it is obtained with high purity, it is preferably in the range of 1 / 0.2 to 1 / 0.5, more preferably in the range of 1 / 0.25 to 1 / 0.45.

The reaction between the phenol compound (a1) and the hydroxyl group-containing aromatic aldehyde compound (a2) is preferably performed under acid catalyst conditions. Examples of the acid catalyst used here include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic 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 paratoluenesulfonic acid are preferable from the viewpoint of excellent catalytic activity.

The reaction of the phenol compound (a1) and the hydroxyl group-containing aromatic aldehyde compound (a2) may be performed in an organic solvent as necessary. Examples of the solvent used here include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, , 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin and other polyols; 2-ethoxyethanol, ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene Glycol ethers such as recall ethyl methyl ether and ethylene glycol monophenyl ether; cyclic ethers such as 1,3-dioxane, 1,4-dioxane and tetrahydrofuran; glycol esters such as ethylene glycol acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone and the like Examples include ketones. These solvents may be used alone or in combination of two or more kinds.

The reaction of the phenol compound (a1) and the hydroxyl group-containing aromatic aldehyde compound (a2) is performed, for example, in a temperature range of 60 to 140 ° C. for 0.5 to 20 hours.

After completion of the reaction, for example, the reaction product is put into a poor solvent (S1) of the tri (hydroxyaryl) alkane type compound (A) and the precipitate is filtered off, and then the tri (hydroxyaryl) alkane type compound ( By the method of redissolving the precipitate obtained in the solvent (S2) that is highly soluble in A) and miscible with the poor solvent (S1), unreacted phenol compound (a1) or hydroxyl group is obtained from the reaction product. The contained aromatic aldehyde compound (a2) and the acid catalyst used can be removed to obtain a purified tri (hydroxyaryl) alkane type compound (A).

When the reaction between the phenol compound (a1) and the hydroxyl group-containing aromatic aldehyde compound (a2) is carried out in an aromatic hydrocarbon solvent such as toluene or xylene, the reaction product is heated to 80 ° C. or higher to A crystal of the tri (hydroxyaryl) alkane type compound (A) can be precipitated by dissolving the (hydroxyaryl) alkane type compound (A) in an aromatic hydrocarbon solvent and cooling it as it is.

The poor solvent (S1) used for purification of the tri (hydroxyaryl) alkane type compound (A) is, for example, water; monoalcohols such as methanol, ethanol, propanol, ethoxyethanol; n-hexane, n-heptane, n -Aliphatic hydrocarbons such as octane and cyclohexane; aromatic hydrocarbons such as toluene and xylene. These may be used alone or in combination of two or more. Of these, water, methanol, and ethoxyethanol are preferred because of the excellent solubility of the acid catalyst.

On the other hand, the solvent (S2) is, for example, a monoalcohol such as methanol, ethanol, or propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentane. Polyols such as diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, 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 dimethyl ether, Glycol ethers such as ethylene glycol ethyl methyl ether and ethylene glycol monophenyl ether; Cyclic ethers such as 1,3-dioxane and 1,4-dioxane; Glycol esters such as ethylene glycol acetate; Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone Etc. These may be used alone or in combination of two or more. Especially, when water or monoalcohol is used as the poor solvent (S1), it is preferable to use acetone as the solvent (S2).

After completion of the reaction, the tri (hydroxyaryl) alkane type compound (A) with higher purity can be obtained by purifying the reaction product by washing with water or reprecipitation. The degree of purification of the tri (hydroxyaryl) alkane type compound (A) is not particularly limited, but the performance of the phenolic hydroxyl group-containing resin such as fluidity, heat resistance, developability, and dry etching resistance is further improved. The purity of the tri (hydroxyaryl) alkane-type compound (A) is preferably 90% or more, more preferably 95% or more as a value calculated from the area ratio in the GPC chart.

In the present invention, the purity of the tri (hydroxyaryl) alkane type compound (A) is a value calculated from the area ratio of the chart obtained by GPC measurement under the following conditions. Further, the molecular weight and polydispersity (Mw / Mn) of the resin described later are values measured by GPC measurement under the following conditions.
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK + “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK + “Shodex KF803” (8.0 mmФ ×) manufactured by Showa Denko KK 300 mm) + “Shodex KF804” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK
Column temperature: 40 ° C
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.30” manufactured by Tosoh Corporation
Developing solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample: Filtered 0.5% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)
Standard sample: Monodispersed polystyrene below (Standard sample: Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
“A-2500” manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
“F-2” manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation

In producing the phenolic hydroxyl group-containing resin of the present invention, the tri (hydroxyaryl) alkane-type compound (A) may be a single structure or a plurality of compounds having different structures. You may use together. Further, other phenolic hydroxyl group-containing compound (A ′) other than the tri (hydroxyaryl) alkane type 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 effects of the present invention are sufficiently exerted. Therefore, the tri (hydroxyaryl) alkane type compound (A) and the other phenolic hydroxyl group-containing compound are used. In a total of 100 parts by mass with (A ′), the tri (hydroxyaryl) alkane type compound (A) is preferably used in a proportion of 70 parts by mass or more, more preferably 90 parts by mass or more. preferable.

The specific structure of the diformylarene compound (B) is not particularly limited as long as it is an aromatic compound having two formyl groups, and any compound may be used. Moreover, the substitution position on the aromatic nucleus of two formyl groups is not particularly limited. Specific examples of the diformylarene compound (B) include, for example, diformylbenzene, diformylnaphthalene, diformylanthracene, and one or more of hydrogen atoms on these aromatic rings are alkyl groups, alkoxy groups, halogen atoms And the like. A diformylarene compound (B) may be used individually by 1 type, and may use multiple types together. Among them, since it becomes a phenolic hydroxyl group-containing resin having an excellent balance of fluidity, heat resistance, and dry etching resistance, one or more of hydrogen atoms on diformylbenzene and its aromatic ring are alkyl groups, alkoxy groups, halogens. A compound substituted with an atom or the like is preferable, and diformylbenzene is more preferable.

In the present invention, in addition to the diformylarene compound (B), other diformyl compounds (B ′) such as diformylalkane, monoformyl compounds (B ″) such as benzaldehyde compounds, naphthaldehyde compounds, monoformylalkanes, etc. When the other diformyl compound (B ′) is used in combination, the effects of the present invention are sufficiently exerted, so that the diformylarene compound is contained in a total of 100 parts by mass of these formyl group-containing compounds. (B) is preferably used in a proportion of 70 parts by mass or more, and more preferably used in a proportion of 90 parts by mass or more.

The reaction method of the tri (hydroxyaryl) alkane type compound (A) and the diformylarene compound (B) is not particularly limited. For example, the reaction can be carried out in the same manner as a general method for producing a novolak resin. .

The reaction molar ratio [(A) / (B)] between the tri (hydroxyaryl) alkane type compound (A) and the diformylarene compound (B) is appropriately adjusted according to the desired molecular weight, etc. Since excessively high molecular weight can be suppressed and a phenolic hydroxyl group-containing resin having a molecular weight suitable as a resist material can be obtained, the range of 1 / 0.1 to 1 / 0.8 is preferable. A range of 3 to 1 / 0.7 is more preferable.

When the other phenolic hydroxyl group-containing compound (A ′), other diformyl compound (B ′) and monoformyl compound (B ″) are used in combination, the total of phenolic hydroxyl group-containing compound raw materials (P) and a formyl group are contained. The reaction molar ratio [(P) / (H)] with the compound (H) is preferably in the range of 1 / 0.1 to 1 / 0.8, and 1 / 0.3 to 1 / 0.7. More preferably, it is the range.

The reaction between the tri (hydroxyaryl) alkane type compound (A) and the diformylarene compound (B) is preferably carried out under acid catalyst conditions. Examples of the acid catalyst used here include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic 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 paratoluenesulfonic acid are preferable from the viewpoint of excellent catalytic activity.

The reaction of the tri (hydroxyaryl) alkane type compound (A) and the diformylarene compound (B) may be performed in an organic solvent as necessary. Examples of the solvent used here include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, , 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin and other polyols; 2-ethoxyethanol, ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene Glycol ethers such as recall ethyl methyl ether and ethylene glycol monophenyl ether; cyclic ethers such as 1,3-dioxane, 1,4-dioxane and tetrahydrofuran; glycol esters such as ethylene glycol acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone and the like Examples include ketones. These solvents may be used alone or in combination of two or more kinds.

The reaction of the tri (hydroxyaryl) alkane type compound (A) and the diformylarene compound (B) is performed, for example, in a temperature range of 60 to 140 ° C. for 0.5 to 20 hours.

After completion of the reaction, the desired phenolic hydroxyl group-containing resin can be obtained by performing reprecipitation operation by adding water to the reaction product.

The weight average molecular weight (Mw) of the phenolic hydroxyl group-containing resin of the present invention is in the range of 3,000 to 50,000 because the phenolic hydroxyl group-containing resin has an excellent balance of fluidity, heat resistance, and dry etching resistance. Is preferable, and the range of 5,000 to 15,000 is more preferable. The polydispersity (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. A range of 0 to 3.5 is particularly preferred.

In the present invention, the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) are values measured by GPC under the following conditions.
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK + “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK
+ Showa Denko Co., Ltd. “Shodex KF803” (8.0 mmФ × 300 mm) + Showa Denko Co., Ltd. “Shodex KF804” (8.0 mmФ × 300 mm)
Column temperature: 40 ° C
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.30” manufactured by Tosoh Corporation
Developing solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample: Filtered 0.5% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)
Standard sample: Monodispersed polystyrene below (Standard sample: Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
“A-2500” manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
“F-2” manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation

The phenolic hydroxyl group-containing resin of the present invention described in detail above can be used for various applications such as paints, adhesives, electric / electronic members, photoresists, liquid crystal alignment films, etc., as in general phenol resins. Above all, it is particularly suitable as a resist material as an application that makes use of characteristics such as fluidity, heat resistance, developability, and dry etching resistance. In addition to general interlayer insulation films, resist underlayer films, resist permanent films, etc. It can be used for various resist members.

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

Examples of the aromatic (poly) hydroxy compound include 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-tri Hydroxybenzophenone, 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′-pentahydroxybenzophenone, 2,2 ′, 3,4,5-pentahydroxybenzophenone, 2,3 ′, 4,4 ', 5', 6-hexahydroxybenzophenone, 2,3,3 ', 4,4', 5'-hexahydroxybenzophenone, etc. Polyhydroxy benzophenone compound;

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′-dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (2 ′, 3 ′, 4′-trihydroxyphenyl) Propane, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1methylethyl] phenyl] ethylidene] bisphenol, 3,3′-dimethyl- {1- [4- [2- ( Bis [(poly) hydroxyphenyl] alkane compounds such as 3-methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol;

Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethyl) A tris (hydroxyphenyl) methane compound such as phenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, or a methyl-substituted product thereof;

Bis (3-cyclohexyl-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-methylphenyl) -3-hydroxyphenylmethane, bis ( 5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3- Methylph Nyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxy Phenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4) -Methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane and the like, bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methane compounds Methyl-substituted products thereof. These photosensitizers may be used alone or in combination of two or more.

The blending amount of the photosensitive agent in the photosensitive composition of the present invention is a photosensitive composition having excellent photosensitivity, and therefore 5 to 50 parts by mass with respect to 100 parts by mass in total of the resin solid content of the photosensitive composition. It is preferable that the ratio is

In addition to the phenolic hydroxyl group-containing resin of the present invention, the photosensitive composition of the present invention may be used in combination with other resins (X). Other resins (X) used here include, for example, various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, Modified novolak resin, phenol aralkyl resin (Xylok resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, biphenyl modified phenol resin, biphenyl modified naphthol resin, aminotriazine modified phenol resin, and various vinyl polymers Etc.

More specifically, the various novolak resins include phenols, alkylphenols such as cresol and xylenol, bisphenols such as phenylphenol, resorcinol, biphenyl, bisphenol A and bisphenol F, and phenolic hydroxyl group-containing compounds such as naphthol and dihydroxynaphthalene. And a polymer obtained by reacting an aldehyde compound with an acid catalyst.

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

When these other resins are used, the blending ratio of the phenolic hydroxyl group-containing resin of the present invention and the other resin (X) can be arbitrarily set according to the use, but the effect of the present invention is more remarkable. Therefore, the proportion of the other resin (X) is preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the phenolic hydroxyl group-containing resin of the present invention.

In addition, taking advantage of the excellent photosensitivity of the phenolic hydroxyl group-containing resin of the present invention and using it as a sensitivity improver, the phenolic hydroxyl group of the present invention is used with respect to 100 parts by mass of the other resin (X). The resin content is preferably in the range of 3 to 80 parts by mass.

The photosensitive composition of the present invention may contain a surfactant for the purpose of improving the film forming property and pattern adhesion when used for resist applications. Examples of the surfactant used here include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ether compounds such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene Polyoxyethylene alkyl allyl ether compounds such as ethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid ester compounds such as polyoxyethylene sorbitan monolaurate, poly Nonionic surfactants such as polyoxyethylene sorbitan fatty acid ester compounds such as xylethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate; fluoro fat Fluorosurfactants having a fluorine atom in the molecular structure such as a copolymer of a polymerizable monomer having a group and [poly (oxyalkylene)] (meth) acrylate; having a silicone structure site in the molecular structure Examples thereof include silicone surfactants. These may be used alone or in combination of two or more.

The compounding amount of these surfactants is preferably in the range of 0.001 to 2 parts by mass with respect to a total of 100 parts by mass of resin solids in the photosensitive composition of the present invention.

When the photosensitive composition of the present invention is used for resist applications, in addition to the phenolic hydroxyl group-containing resin and photosensitive agent of the present invention, other resins (X), surfactants, dyes, and fillers as necessary. A photosensitive resist material can be obtained by adding various additives such as a crosslinking agent and a dissolution accelerator and dissolving in an organic solvent. The photosensitive resist material may be used as it is as a coating material, or may be used as a resist film obtained by applying a photosensitive resist material on a support film and removing the solvent. Examples of the support film used as a resist film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate, and may be a single layer film or a plurality of laminated films. The surface of the support film may be a corona-treated one or a release agent.

The type of the organic solvent is not particularly limited. For example, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether propylene glycol monomethyl ether; diethylene glycol dimethyl ether, diethylene glycol Dialkylene glycol dialkyl ethers such as diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; alkylene glycol alkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate Acetate; ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone; cyclic ethers such as dioxane; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethoxyacetic acid Ethyl, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate, etc. These may be ester compounds, and these 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. When the resist material contains a filler or a pigment, it can be produced by dispersing or mixing using a dispersing device such as a dissolver, a homogenizer, or a three roll mill.

Examples of a general photolithography method using the photosensitive resist material include the following methods. First, the photosensitive resist material is applied onto an object to be subjected to photolithography such as a silicon substrate, a silicon carbide substrate, a gallium nitride substrate, and prebaked at a temperature of 60 to 150 ° C. The coating method at this time may be any method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor blade coating and the like. Next, the resist pattern is formed by exposing through a resist pattern and developing with an alkali developer.

When the photosensitive resist material is used for a resist permanent film, it is preferable to contain a crosslinking agent in addition to the photosensitive agent. Examples of the crosslinking agent used here are the same as those used in the curable composition described below. Examples of the method for forming the resist permanent film include the following methods. First, the photosensitive resist material is applied on an object such as a silicon substrate, a silicon carbide substrate, a gallium nitride substrate and the like to be subjected to photolithography, and prebaked at a temperature of 60 to 150 ° C. The application method is the same as that described above. Next, the resist pattern is exposed to light, further thermally cured at a temperature of 110 to 210 ° C., and then developed with an alkali developer to form a resist pattern. Alternatively, after exposure, the film may be developed with an alkali developer first, and then thermally cured at a temperature of 110 to 210 ° C.

Specific examples of the resist permanent film include a solder resist, a package material, an underfill material, a package adhesive layer of a circuit element, and an adhesive layer between a product circuit element and a circuit board in a semiconductor device. In thin displays represented by LCD and OELD, there are a thin film transistor protective film, a liquid crystal color filter protective film, a black matrix, a spacer, and the like.

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. In addition to the phenolic hydroxyl group-containing resin of the present invention, other resins (Y) may be used in combination. Other resins (Y) used here include, for example, various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, Modified novolak resin, phenol aralkyl resin (Xylok resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, biphenyl modified phenol resin, biphenyl modified naphthol resin, aminotriazine modified phenol resin, and various vinyl polymers Etc.

More specifically, the various novolak resins include phenolphenol, cresol, xylenol and other alkylphenols, phenylphenol, resorcinol, biphenyl, bisphenols such as bisphenol A and bisphenol F, phenolic hydroxyl group-containing compounds such as naphthol and dihydroxynaphthalene. And a polymer obtained by reacting an aldehyde compound with acid catalyst conditions.

When these other resins are used, the blending ratio of the phenolic hydroxyl group-containing resin of the present invention and the other resin (Y) can be arbitrarily set according to the use, but the effect of the present invention is more remarkable. Therefore, the ratio of the other resin (Y) to 0.5 to 100 parts by mass with respect to 100 parts by mass of the phenolic hydroxyl group-containing resin of the present invention is preferable.

The curing agent used in the present invention is not particularly limited as long as it is a compound capable of causing 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 according to the type of curing agent or the type of curing accelerator described below. it can. Curing conditions such as the heating temperature and time in thermosetting, the type of light beam in photocuring and the exposure time are appropriately adjusted according to the type of curing agent, the type of curing accelerator described below, and the like.

Specific examples of the curing agent include, for example, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, resol resins, epoxy compounds, isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, acid anhydrides, and the like. Products, oxazoline compounds and the like.

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

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

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

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

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

Examples of the epoxy compound include diglycidyloxynaphthalene, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, Phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane, naphthylene ether type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene- Examples include phenol addition reaction type epoxy resins, phosphorus atom-containing epoxy resins, polyglycidyl ethers of cocondensates of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, and the like. That.

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

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

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

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

Among these, a glycoluril compound, a urea compound, and a resole resin are preferable, and a glycoluril compound is particularly preferable because it is a curable composition having excellent curability and heat resistance in a cured product.

Since the compounding quantity of the said hardening | curing agent in the curable composition of this invention becomes a composition excellent in sclerosis | hardenability, with respect to a total of 100 mass parts of phenolic hydroxyl group containing resin of this invention, and other resin (X). The ratio is preferably 0.5 to 50 parts by mass.

The curable composition of the present invention may contain a curing accelerator together with the curing agent. When 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, paratoluenesulfonic acid, zinc acetate, manganese acetate is used as a curing accelerator. Is preferred. 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-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium bis (perfluorobutanesulfonyl) imide, bis [4-n-alkylphenyl] iodonium salt compounds such as iodonium tetrakispentafluorophenylborate (n-alkyl groups in each compound are preferably those having 10 to 13 carbon atoms); 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) And chloromethyltriazine compounds such as -s-triazine and 2- [2- (3,4-dimethoxyphenyl) ethynyl] -4,6-bis (trichloromethyl) -s-triazine. The curing accelerators may be used alone or in combination of two or more. The addition amount of the curing accelerator is preferably in the range of 0.1 to 10% by mass with respect to the resin solid content of the curable composition.

When the curable composition of the present invention is used for resist applications, in addition to the phenolic hydroxyl group-containing resin and the curing agent of the present invention, other resins (Y), surfactants, dyes, and fillers as necessary. A curable resist material can be obtained by adding various additives such as a crosslinking agent and a dissolution accelerator and dissolving in an organic solvent. The curable resist material may be used as it is as a coating material, or a curable resist material applied on a support film and desolvated may be used as a resist film. Examples of the support film used as a resist film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate, and may be a single layer film or a plurality of laminated films. The surface of the support film may be a corona-treated one or a release agent.

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

When the curable resist material is used for a resist underlayer film application, as an example of a method for forming the resist underlayer film, for example, the curable resist material is subjected to photolithography such as a silicon substrate, a silicon carbide substrate, a gallium nitride base, etc. A resist underlayer film is formed by a method such as coating on a product, drying under a temperature condition of 100 to 200 ° C., and further heat curing under a temperature condition of 250 to 400 ° C. Next, a resist pattern is formed on this lower layer film by performing a normal photolithography operation, and a resist pattern by a multilayer resist method can be formed by performing a dry etching process with a halogen-based plasma gas or the like.

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

In the examples of the present application, the purity of the tri (hydroxyaryl) alkane type compound (A-1) is a value calculated from the area ratio of the chart obtained by GPC measurement under the following conditions. Further, the number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity (Mw / Mn) of the synthesized resin are measured under the following GPC measurement conditions.
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK + “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK
+ Showa Denko Co., Ltd. “Shodex KF803” (8.0 mmФ × 300 mm) + Showa Denko Co., Ltd. “Shodex KF804” (8.0 mmФ × 300 mm)
Column temperature: 40 ° C
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.30” manufactured by Tosoh Corporation
Developing solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample: 0.5% by mass tetrahydrofuran solution filtered with a microfilter in terms of resin solids Injection volume: 0.1 mL
Standard sample: Monodispersed polystyrene below (Standard sample: Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
“A-2500” manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
“F-2” manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation

^{The 13} C-NMR spectrum was measured under the following conditions.
Measuring device: “AL-400” manufactured by JEOL Ltd.
Solvent: DMSO-d ₆
Sample concentration: 30 wt%
Measurement mode: SGNNE (1H complete decoupling method of NOE elimination)
Pulse angle: 45 ° C pulse Integration count: 10,000 times

Production Example 1 Production of tri (hydroxyaryl) alkane-type compound (A-1) A 2000 ml four-necked flask equipped with a condenser was charged with 293.2 g of 2,5-xylenol and 122 g of 4-hydroxybenzaldehyde, and 2-ethoxy Dissolved in 500 ml of ethanol. After adding 30 ml of sulfuric acid while cooling in an ice bath, the mixture was heated to 100 ° C. with a mantle heater and reacted with stirring for 2 hours. After completion 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 reprecipitated by adding water again. The precipitate was filtered off and dried under vacuum to obtain 213 g of white crystalline tri (hydroxyaryl) alkane type compound (A-1). The purity of the tri (hydroxyaryl) alkane type compound (A-1) calculated from the area ratio in the GPC chart was 98.2%. A GPC chart of the tri (hydroxyaryl) alkane type compound (A-1) is shown in FIG. 1, and a ¹³ C-NMR chart is shown in FIG.

Example 1 Production of phenolic hydroxyl group-containing resin (1) A 100 ml four-necked flask equipped with a cooling tube was charged with 18.3 g of tri (hydroxyaryl) alkane type compound (A-1) and 3.6 g of terephthalaldehyde. -54.9 g of ethoxyethanol was added and dissolved. After adding 2.8 g of 98 wt% sulfuric acid, the mixture was heated to 100 ° C. and reacted for 14 hours. After completion of the reaction, water was added to the resulting reaction mixture to precipitate a crude product. The recovered crude product was dissolved in acetone and reprecipitated by adding water again. The precipitate was separated by filtration and vacuum-dried to obtain 20.2 g of a red powdery phenolic hydroxyl group-containing resin (1). The number average molecular weight (Mn) of the phenolic hydroxyl group-containing resin (1) was 2,828, the weight average molecular weight (Mw) was 7,905, and the polydispersity (Mw / Mn) was 2.80. A GPC chart of the phenolic hydroxyl group-containing resin (1) is shown in FIG.

Example 2 Production of phenolic hydroxyl group-containing resin (2) A 100 ml four-necked flask equipped with a cooling tube was charged with 18.3 g of a tri (hydroxyaryl) alkane-type compound (A-1) and 3.6 g of isophthalaldehyde. 54.9 g of ethoxyethanol was added and dissolved. After adding 2.8 g of 98 wt% sulfuric acid, the mixture was heated to 100 ° C. and reacted for 14 hours. After completion of the reaction, water was added to the resulting reaction mixture to precipitate a crude product. The recovered crude product was dissolved in acetone and reprecipitated by adding water again. The precipitate was separated by filtration and vacuum-dried to obtain 20.5 g of a red powdery phenolic hydroxyl group-containing resin (2). The number average molecular weight (Mn) of the phenolic hydroxyl group-containing resin (2) was 3,267, the weight average molecular weight (Mw) was 9,975, and the polydispersity (Mw / Mn) was 3.05. FIG. 4 shows a GPC chart of the phenolic hydroxyl group-containing resin (2).

Comparative Production Example 1 Production of phenolic hydroxyl group-containing resin (1 ′) In a 2 L 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, 492 g of 42% formaldehyde And heated to 100 ° C. for reaction. The mixture was heated to 200 ° C. at normal pressure, dehydrated and distilled, and further distilled under reduced pressure at 230 ° C. for 6 hours to obtain 736 g of a pale yellow solid phenolic hydroxyl group-containing resin (1 ′). The number average molecular weight (Mn) of the phenolic hydroxyl group-containing resin (1 ′) was 1,450, the weight average molecular weight (Mw) was 10,316, and the polydispersity (Mw / Mn) was 7.12.

Examples 3 and 4 and Comparative Example 1
The phenolic hydroxyl group-containing resins obtained in Examples 1 and 2 and Comparative Production Example 1 were evaluated in the following manner. The results are shown in Table 1.

Production 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 photosensitizing agent was added to the solution and dissolved. This was filtered through a 0.2 μm membrane filter to obtain a photosensitive composition.
The photosensitizer was “P-200” (4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1methylethyl] phenyl] ethylidene] bisphenol, 1 mol 2-naphthoquinone-2-diazide-5-sulfonyl chloride condensate).

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

Evaluation of Alkali Developability [ADR (nm / s)] The photosensitive composition obtained above was applied on a 5-inch silicon wafer with a spin coater so as to have a thickness of about 1 μm. Dried for 60 seconds. Two wafers were prepared, and one of them was designated as “no exposure sample”. The other was used as an “exposed sample” and irradiated with 100 mJ / cm ² of ghi line using a ghi line lamp (“Multi Light” manufactured by USHIO INC.), And then heat-treated at 140 ° C. for 60 seconds. .
Both the “non-exposed sample” and the “exposed sample” were immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds and then dried on a hot plate at 110 ° C. for 60 seconds. The film thickness of each sample before and after immersion in the 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 so as to have a thickness of about 1 μm, and dried on a hot plate at 110 ° C. for 60 seconds. 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 every 1 μm is brought into close contact with this wafer, and then a ghi line lamp (“Multi Light” manufactured by USHIO INC. )) Was used for irradiation with ghi rays, and heat treatment was performed at 140 ° C. for 60 seconds. Next, the film was immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and then dried on a hot plate at 110 ° C. for 60 seconds.
The exposure amount (Eop exposure amount) capable of faithfully reproducing the line width of 3 μm when the ghi line exposure amount was increased from 100 mJ / cm ² to 10 mJ / cm ² was evaluated.

Evaluation of Resolution The photosensitive composition obtained above was applied onto a 5-inch silicon wafer with 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 is placed on the obtained wafer and irradiated with 200 mJ / cm ² of ghi line using a ghi line lamp (“Ushio Electric Co., Ltd.“ Multi-light ”), and then heat-treated at 140 ° C. for 60 seconds. Went. Next, the film was immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and then dried on a hot plate at 110 ° C. for 60 seconds. The pattern state is confirmed using a laser microscope (Keyence Co., Ltd. “VK-X200”). A / L / S = 1, where the line width of L / S = 1/1 is resolved at 5 μm. A line width of 1 was evaluated as B when the line width was 5 μm and could not be resolved.

Evaluation of heat resistance The composition for heat resistance test obtained above was applied onto a 5-inch silicon wafer with 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 content was scraped from the obtained wafer and the glass transition temperature (Tg) was measured. The glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC) (“Q100” manufactured by TA Instruments Co., Ltd.) under a nitrogen atmosphere, a temperature range of −100 to 250 ° C., and a temperature rising temperature of 10 ° C. / Performed under the condition of minutes.

Examples 5 and 6 and Comparative Example 2
The phenolic hydroxyl group-containing resins obtained in Examples 1 and 2 and Comparative Production Example 1 were evaluated in the following manner. The results are shown in Table 2.

Production of curable 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 this was filtered through a 0.2 μm membrane filter to obtain a curable composition. Got.
As the curing agent, “1,3,4,6-tetrakis (methoxymethyl) glycoluril” manufactured by Tokyo Chemical Industry Co., Ltd. was used.

Evaluation of Alkali Developability [ADR (nm / s)] The curable composition obtained above was applied on a 5-inch silicon wafer with a spin coater so as to have a thickness of about 1 μm. Dried for 60 seconds. This was immersed in an alkali developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and then dried on a hot plate at 110 ° C. for 60 seconds. The film thickness before and after immersion in the developer was measured, and the value obtained by dividing the difference by 60 was defined as alkali developability [ADR (nm / s)].

Evaluation of dry etching resistance The curable composition obtained above was applied onto a 5-inch silicon wafer with a spin coater and dried on a hot plate at 180 ° C. for 60 seconds in an environment with an oxygen concentration of 20% by volume. Subsequently, it was heat-cured at 350 ° C. for 120 seconds to form a cured coating film having a thickness of 0.3 μm. The cured coating film on the wafer was subjected to CF ₄ / Ar / O ₂ (CF ₄ : 40 mL / min, Ar: 20 mL / min, O ₂ : 5 mL) using an etching apparatus (“EXAM” manufactured by Shinko Seiki Co., Ltd.). / Min Pressure: 20 Pa RF power: 200 W Processing time: 40 seconds Temperature: 15 ° C.) Etching was performed. The film thickness before and after the etching treatment at this time was measured, the etching rate was calculated, and the etching resistance was evaluated. The evaluation criteria are as follows.
A: When the etching rate is 150 nm / min or less B: When the etching rate exceeds 150 nm / min

Evaluation of fluidity The curable composition obtained above was applied by a spin coater onto a silicon wafer having a diameter of 5 inches and a hole pattern having a diameter of 110 nm and a depth of 300 nm. After drying on a hot plate at 180 ° C. for 180 seconds, heat curing was carried out at 210 ° C. for 60 seconds to obtain a cured coating film having a film thickness of 0.3 μm. A silicon wafer is cut on a hole pattern line, and a cross section is observed with a laser microscope (Keyence Co., Ltd. “VK-X200”) to evaluate whether the flow of the curable composition into the hole pattern was sufficient under the following conditions. did.
A: The whole hole is filled with the cured product B: The whole hole is not filled with the cured product and there is a gap.

Claims

A phenolic hydroxyl group-containing resin which is a reaction product of a tri (hydroxyaryl) alkane type compound (A) and a diformylarene compound (B).
The tri (hydroxyaryl) alkane type compound (A) is represented by the following structural formula (1-1) or (1-2):

[Wherein R 1 and R 2 are each independently an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group or a halogen atom. l is independently 0 or an integer of 1 to 4, m is 0 or an integer of 1 to 4, and n is 0 or an integer of 1 to 6. R 3 is a hydrogen atom or an alkyl group. ]
The phenolic hydroxyl group-containing resin according to claim 1, which is a compound represented by the formula:
The phenolic hydroxyl group-containing resin according to claim 1, wherein the polydispersity (Mw / Mn) is in the range of 1.1 to 10.0.
A photosensitive composition comprising the phenolic hydroxyl group-containing resin according to any one of claims 1 to 3 and a photosensitive agent.
A curable composition comprising the phenolic hydroxyl group-containing resin according to any one of claims 1 to 3 and a curing agent.
A cured product of the curable composition according to claim 5.
A resist material using the phenolic hydroxyl group-containing resin according to any one of claims 1 to 3.