KR102419372B1 - Phenolic hydroxyl group-containing resin and resist material - Google Patents

Abstract

[식 중 R², R³은 각각 독립으로 지방족 탄화수소기, 방향환 함유 탄화수소기, 알콕시기, 할로겐 원자 중 어느 하나이다]
으로 표시되는 구조 부위(α)와, 하기 구조식(3)

(식 중 R⁴은 수소 원자 또는 탄소 원자수 1∼7의 지방족 탄화수소기이다. R⁵은 수소 원자 또는 탄소 원자수 8∼24의 지방족 탄화수소기이다)
으로 표시되는 구조 부위(β)를 반복 단위로서 갖고, 수지 중에 존재하는 R², R³, R⁵ 중 적어도 하나가 탄소 원자수 8∼24의 지방족 탄화수소기인 것을 특징으로 하는 페놀성 수산기 함유 수지를 제공한다.In addition to heat resistance and alkali developability, for the purpose of providing a phenolic hydroxyl group-containing resin excellent in crack resistance at the time of forming a thick film, a photosensitive composition containing the same, a curable composition, and a resist material, the following structural formula (1) or (2)

[Wherein, R ² and R ³ are each independently any one of an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, and a halogen atom]
The structural moiety (α) represented by and the following structural formula (3)

(wherein R ⁴ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 7 carbon atoms. R ⁵ is a hydrogen atom or an aliphatic hydrocarbon group having 8 to 24 carbon atoms)
^{A phenolic} hydroxyl group ^- containing resin having a structural moiety (β) represented by to provide.

Description

Phenolic hydroxyl group-containing resin and resist material

The present invention relates to a phenolic hydroxyl group-containing resin excellent in heat resistance and alkali developability as well as crack resistance at the time of forming a thick film, a photosensitive composition containing the same, a curable composition, and a resist material.

In the field of photoresists, a variety of resist pattern formation methods subdivided according to uses and functions are being developed one after another, and with it, the performance required for a resin material for resist is also being advanced and diversified. For example, a resin material for pattern formation is required to have high developability for accurately forming fine patterns on highly integrated semiconductors and with high production efficiency. In applications called underlayer films, anti-reflection films, BARC films, hard masks, etc., in addition to dry etching resistance and low reflectivity, in the most advanced fields, thick films of several tens of microns can be formed, and cracks or cracks are required. In addition to high heat resistance, in applications called resist permanent films, etc., it is required that a thick film can be formed, that deterioration with time does not occur, and the like. In addition, from the viewpoint of quality reliability, long-term storage stability under various environments around the world is also an important performance.

The most widely used phenolic hydroxyl group-containing resin for photoresist applications is a cresol novolak type, but it cannot respond to the performance demanded by the market in recent years with advancement and diversification, and heat resistance and developability are not sufficient. Since cracks occur when a thick film is formed, it cannot be used for thick film applications (refer to Patent Document 1).

Japanese Patent Application Laid-Open No. 2-55359

Accordingly, the problem to be solved by the present invention is to provide a phenolic hydroxyl group-containing resin excellent in heat resistance and alkali developability as well as crack resistance during thick film formation, a photosensitive composition containing the same, a curable composition, and a resist material.

MEANS TO SOLVE THE PROBLEM The present inventors made earnest examination in order to solve the said subject, As a result, a triarylmethane type phenolic hydroxyl group containing compound and a novolak resin which uses phenol or a phenol compound which has a C1-C7 aliphatic hydrocarbon group as reaction raw materials. The phenolic hydroxyl group-containing resin obtained by reacting an intermediate with an alkene compound having 8 to 24 carbon atoms was found to be excellent in heat resistance and alkali developability, and also excellent in crack resistance at the time of forming a thick film, leading to the completion of the present invention.

That is, the present invention, the following structural formula (1) or (2)

[In the formula, R ¹ is any one of a hydrogen atom, an aliphatic hydrocarbon group, and an aromatic ring-containing hydrocarbon group. k is any one of 0, 1, or 2. R ² and R ³ are each independently any one of an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, and a halogen atom, l is each independently 0 or an integer of 1 to 4, m is 0 or 1 to 5 An integer and n are 0 or an integer of 1-7. * is a point of bonding with the illustrated benzene ring or naphthalene ring, and both * may be bonded to the same aromatic ring or may be bonded to different aromatic rings]

The structural moiety (α) represented by and the following structural formula (3)

(Wherein, R ¹ is any one of a hydrogen atom, an aliphatic hydrocarbon group, and an aromatic ring-containing hydrocarbon group. R ⁴ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 7 carbon atoms. R ⁵ is a hydrogen atom or an aliphatic hydrocarbon group having 8 carbon atoms. -24 is an aliphatic hydrocarbon group)

^{A phenolic} hydroxyl group ^- containing resin having a structural moiety (β) represented by it's about

The present invention also has the following structural formula (4) or (5)

[In the formula, k is any one of 0, 1, and 2. R ² and R ³ are each independently any one of an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, and a halogen atom, l is each independently 0 or an integer of 1 to 4, m is 0 or 1 to 5 An integer, n is 0 or an integer of 1-7]

A novolak resin intermediate using a triarylmethane compound (A) having a molecular structure represented by , a phenol compound (B) having a phenol or aliphatic hydrocarbon group having 1 to 7 carbon atoms, and an aldehyde compound (C) as reaction raw materials It relates to a phenolic hydroxyl group-containing resin which is a reaction product of (M) and an alkene compound (D) having 8 to 24 carbon atoms.

The present invention also relates to a photosensitive composition comprising the phenolic hydroxyl group-containing resin and a photosensitizer.

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

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

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

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

ADVANTAGE OF THE INVENTION According to this invention, in addition to heat resistance and alkali developability, the phenolic hydroxyl-containing resin excellent also in the crack resistance at the time of thick film formation, a photosensitive composition containing this, a curable composition, and a resist material can be provided.

1 is a GPC chart of the triarylmethane type compound (A-1) obtained in Production Example 1. FIG.
Fig. 2 is a ¹³ C-NMR chart of the triarylmethane-type compound (A-1) obtained in Production Example 1.
3 is a GPC chart diagram of phenolic hydroxyl group-containing resin (1) obtained in Example 1. FIG.
4 is a GPC chart diagram of phenolic hydroxyl group-containing resin (2) obtained in Example 2. FIG.
5 is a GPC chart diagram of phenolic hydroxyl group-containing resin (3) obtained in Example 3. FIG.
6 is a GPC chart diagram of phenolic hydroxyl group-containing resin (4) obtained in Example 4.
Fig. 7 is a GPC chart diagram of phenolic hydroxyl group-containing resin (5) obtained in Example 5;

Hereinafter, the present invention will be described in detail.

The phenolic hydroxyl group-containing resin of the present invention has the following structural formula (1) or (2)

[In the formula, R ¹ is any one of a hydrogen atom, an aliphatic hydrocarbon group, and an aromatic ring-containing hydrocarbon group. k is any one of 0, 1, or 2. R ² and R ³ are each independently any one of an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, and a halogen atom, l is each independently 0 or an integer of 1 to 4, m is 0 or 1 to 5 An integer and n are 0 or an integer of 1-7. * is a point of bonding with the illustrated benzene ring or naphthalene ring, and both * may be bonded to the same aromatic ring or may be bonded to different aromatic rings]

The structural moiety (α) represented by and the following structural formula (3)

(Wherein, R ¹ is any one of a hydrogen atom, an aliphatic hydrocarbon group, and an aromatic ring-containing hydrocarbon group. R ⁴ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 7 carbon atoms. R ⁵ is a hydrogen atom or an aliphatic hydrocarbon group having 8 carbon atoms. -24 is an aliphatic hydrocarbon group)

It has a structural moiety (β) represented by , as a repeating unit, and at least one of R ² , R ³ , and R ⁵ present in the resin is an aliphatic hydrocarbon group having 8 to 24 carbon atoms.

The phenolic hydroxyl group-containing resin of the present invention has high symmetry and rigid structural moiety (α) as a repeating unit, and has a high density of phenolic hydroxyl groups, and thus has high heat resistance and excellent developability. In the present invention, heat resistance and developability are improved by adopting a resin design in which, in addition to the structural moiety (α), the structural moiety (β) is a repeating unit, and introducing an aliphatic hydrocarbon group having 8 to 24 carbon atoms into the resin structure. It has succeeded in improving the crack resistance at the time of forming a thick film while maintaining it. In general, methods of increasing the flexibility and toughness of the resin by introducing a long-chain aliphatic hydrocarbon group into the resin structure have an effect on improving crack resistance, but a decrease in developability and a decrease in heat resistance accompanying a decrease in the density of functional groups Although it is normal to generate|occur|produce, in this invention, the trade-off of such an effect does not generate|occur|produce, and it becomes a phenolic hydroxyl-containing resin excellent in any of developability, heat resistance, and crack resistance.

R ¹ in the structural formulas (1), (2) and (3) is any one of a hydrogen atom, an aliphatic hydrocarbon group, and an aromatic ring-containing hydrocarbon group. The aliphatic hydrocarbon group is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, an alkyl group of a nonyl group, etc.; A C1-C9 alkyl group etc. are mentioned. Examples of the aromatic ring-containing hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, and a structural moiety in which an alkyl group, an alkoxy group, or a halogen atom is substituted on their aromatic nucleus. have. Especially, since it becomes a phenolic hydroxyl-containing resin excellent in the balance of developability, heat resistance, and crack resistance, it is preferable that R< ¹ > is a hydrogen atom or a C1-C6 alkyl group, and it is more preferable that it is a hydrogen atom.

With respect to the structural moiety (α), * in the structural formulas (1) and (2) is a bonding point with any one of the three aromatic rings shown in the structural formulas (1) and (2), and both * are in the same direction You may couple|bond with the ring, and you may couple|bond with each mutually different aromatic ring. Specific examples of the structural moiety represented by the structural formula (1) include those represented by any one of the following structural formulas (1-1) to (1-4). In addition, the structural moiety represented by the structural formula (2) may specifically include those represented by any one of the following structural formulas (2-1) to (2-4).

[In the formula, R ¹ is any one of a hydrogen atom, an aliphatic hydrocarbon group, and an aromatic ring-containing hydrocarbon group. k is any one of 0, 1, or 2. R ² and R ³ are each independently any one of an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, and a halogen atom, l is each independently 0 or an integer of 1 to 4, m is 0 or 1 to 5 is an integer]

[In the formula, R ¹ is any one of a hydrogen atom, an aliphatic hydrocarbon group, and an aromatic ring-containing hydrocarbon group. k is any one of 0, 1, or 2. R ² , R ³ are each independently any one of an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, and a halogen atom, l is each independently 0 or an integer of 1 to 4, n is 0 or 1 to 7 is an integer]

In the phenolic hydroxyl group-containing resin of the present invention, all of the structural moieties (α) present in the resin may have the same structure, or may have a plurality of structures different from each other. Especially, since it becomes a phenolic hydroxyl-containing resin excellent in the balance of developability, heat resistance, and crack resistance, it is preferable to have a structural site|part represented by the said structural formula (1). Moreover, it is preferable that the value of k in the said structural formula (1), (2) is 1. When k is 1, it is preferable that all of the bonding positions of the three phenolic hydroxyl groups in the structural formula (1) are para-positions with respect to the methine groups that node the three aromatic rings.

R ² in the structural formulas (1) and (2) is each independently any one of an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, and a halogen atom, and l is each independently 0 or an integer of 1-4. The aliphatic hydrocarbon group may be either a straight-chain group or a branched structure, and may have an unsaturated group or not have an unsaturated group in the structure. The number of carbon atoms is not particularly limited, and either a short-chain one having 1 to 6 carbon atoms or a relatively long-chain one having 7 or more carbon atoms may be used. The specific structure of the aromatic ring-containing hydrocarbon group is not particularly limited as long as it is a structural moiety containing an aromatic ring, and in addition to aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, and anthryl group, benzyl group, phenylethyl group, phenyl group Aralkyl groups, such as a propyl group and a naphthylmethyl group, etc. are mentioned. 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, since the phenolic hydroxyl group-containing resin is excellent in the balance of developability, heat resistance, and crack resistance, l is an integer of 2 to 4, among which R ² is an alkyl group having 1 to 3 carbon atoms, and other R It is preferable that ² is a hydrogen atom or a C8-C24 aliphatic hydrocarbon group. Moreover, it is preferable that both R< ² > which is a C1-C3 alkyl group couple|bonded with the 2,5-position of a phenolic hydroxyl group.

R ³ in the structural formulas (1) and (2) is each independently any one of an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, and a halogen atom, m is 0 or an integer of 1 to 5, n is 0 or It is an integer from 1 to 7. The aliphatic hydrocarbon group may be either a straight-chain group or a branched structure, and may have an unsaturated group or not have an unsaturated group in the structure. The number of carbon atoms is not particularly limited, and either a short-chain one having 1 to 6 carbon atoms or a relatively long-chain one having 7 or more carbon atoms may be used. The specific structure of the aromatic ring-containing hydrocarbon group is not particularly limited as long as it is a structural moiety containing an aromatic ring, and in addition to aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, and anthryl group, benzyl group, phenylethyl group, phenyl group Aralkyl groups, such as a propyl group and a naphthylmethyl group, etc. are mentioned. 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. Especially, since it becomes a phenolic hydroxyl-containing resin excellent in the balance of developability, heat resistance, and crack resistance, it is preferable that R< ³ > is a hydrogen atom or a C9-C24 aliphatic hydrocarbon group.

With respect to the structural moiety (β), R ⁴ in the structural formula (3) is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 7 carbon atoms, and R ⁵ is a hydrogen atom or an aliphatic hydrocarbon group having 8 to 24 carbon atoms. These aliphatic hydrocarbon groups may be either linear or branched, and may be either straight-chain or not having an unsaturated group in the structure. Especially, since it becomes a phenolic hydroxyl-containing resin excellent in the balance of developability, heat resistance, and crack resistance, it is preferable that R< ⁴ > is a C1-C4 aliphatic hydrocarbon group, and it is preferable that it is a methyl group. Moreover, it is preferable that the substitution position is a meta position with respect to a phenolic hydroxyl group.

In the phenolic hydroxyl group-containing resin of the present invention, the abundance ratio of the structural moiety (α) to the structural moiety (β) is suitably changed according to the desired resin performance, use, and the like. Especially, since it becomes a phenolic hydroxyl group-containing resin excellent in the balance of developability, heat resistance, and crack resistance, it is preferable that the abundance ratio of both [(α)/(β)] is in the range of 90/10 to 30/70, It is more preferable that it is the range of 80/20-40/60.

In the phenolic hydroxyl group-containing resin of the present invention, at least one of R ² , R ³ , and R ⁵ present in the resin is an aliphatic hydrocarbon group having 8 to 24 carbon atoms. As described above, the aliphatic hydrocarbon group may be either a straight-chain group or a branched structure, or may have an unsaturated group or not have an unsaturated group in the structure. Especially, since it becomes a phenolic hydroxyl-containing resin excellent in the balance of developability, heat resistance, and crack resistance, it is preferable that it is a C8-20 aliphatic hydrocarbon group. Moreover, it is preferable that the structure is a linear alkyl group.

The abundance ratio of the aliphatic hydrocarbon group having 8 to 24 carbon atoms makes the phenolic hydroxyl group-containing resin excellent in the balance of developability, heat resistance and crack resistance. It is preferable that it is a ratio used as 0.5-30 mass % of aliphatic hydrocarbon groups of 24.

Although the method for producing the phenolic hydroxyl group-containing resin of the present invention is not particularly limited, for example, the following structural formula (4) or (5)

[In the formula, k is any one of 0, 1, and 2. R ² and R ³ are each independently any one of an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, and a halogen atom, l is each independently 0 or an integer of 1 to 4, m is 0 or 1 to 5 An integer, n is 0 or an integer of 1-7]

A novolak resin intermediate using a triarylmethane compound (A) having a molecular structure represented by , a phenol compound (B) having a phenol or aliphatic hydrocarbon group having 1 to 7 carbon atoms, and an aldehyde compound (C) as reaction raw materials It can manufacture by the method of making (M) and a C8-C24 alkene compound (D) react.

The said triarylmethane type compound (A) may use individually the thing of the same structure, and may use together several compounds which have mutually different molecular structures. Especially, since it becomes a phenolic hydroxyl-containing resin excellent in the balance of developability, heat resistance, and crack resistance, it is preferable to have a molecular structure represented by the said structural formula (4). In addition, it is preferable that the value of k is 1. When the value of k is 1, in Structural Formula (4), it is preferable that the bonding position of three phenolic hydroxyl groups in a molecular structure is a para position with respect to the methine group which node the three aromatic rings.

Examples of the triarylmethane compound (A) include those obtained by a condensation reaction between a phenol compound (a1) and an aromatic aldehyde compound (a2). Examples of the phenol compound (a1) include phenol and compounds in which one or more hydrogen atoms on the aromatic nucleus of the phenol are substituted with an alkyl group, an alkoxy group, or a halogen atom. These may be used independently, respectively, and may use 2 or more types together. Among them, a compound having any one of an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, and a halogen atom at the 2,5-position of phenol is preferable because it becomes a phenolic hydroxyl group-containing resin excellent in heat resistance, and 2,5 Compounds having an alkyl group having 1 to 3 carbon atoms in the -position are preferred, and 2,5-xylenol is particularly preferred.

The aromatic aldehyde compound (a2) is, for example, a compound having a formyl group on an aromatic nucleus such as benzene, naphthalene, phenol, resorcin, naphthol, dihydroxynaphthalene, an alkyl group, an alkoxy group, The compound which has a halogen atom etc. is mentioned. These may be used independently, respectively, and may use 2 or more types together. Especially, since it becomes phenolic hydroxyl-containing resin excellent in the balance of heat resistance and developability, what has a benzene ring structure is preferable. Specifically, benzaldehyde, salicylaldehyde, m-hydroxybenzaldehyde and p-hydroxybenzaldehyde are preferable, and salicylaldehyde, m-hydroxybenzaldehyde and p-hydroxybenzaldehyde are more preferable.

The reaction molar ratio [(a1)/(a2)] of the phenol compound (a1) and the aromatic aldehyde compound (a2) is 1 It is preferable that it is the range of /0.2-1/0.5, and it is more preferable that it is the range of 1/0.25-1/0.45.

The reaction between the phenol compound (a1) and the aromatic aldehyde compound (a2) is preferably performed under acid catalyst conditions. Examples of the acid catalyst used herein include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts may be used individually, respectively, and may use 2 or more types together. Among these, sulfuric acid and para-toluenesulfonic acid are preferable from the viewpoint of excellent catalytic activity.

You may perform reaction of a phenol compound (a1) and an aromatic aldehyde compound (a2) in an organic solvent as needed. The solvent used here is, for example, monoalcohol, such as methanol, ethanol, and a propanol; Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol polyols such as , 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, and 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, ethylene glycol ethyl methyl ether, ethylene glycol mono glycol ethers such as phenyl ether; cyclic ethers such as 1,3-dioxane, 1,4-dioxane, and tetrahydrofuran; glycol esters such as ethylene glycol acetate; Ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, etc. are mentioned. These solvents may be used independently, respectively, and may be used as 2 or more types of mixed solvent.

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

After completion of the reaction, for example, the reaction product is poured into a poor solvent (S1) of the triarylmethane-type compound (A), the precipitate is separated by filtration, and then the triarylmethane-type compound (A) By a method of re-dissolving the precipitate obtained in the solvent (S2) miscible with the poor solvent (S1), the unreacted phenol compound (a1) or aromatic aldehyde compound (a2) from the reaction product, By removing the used acid catalyst, a purified triarylmethane type compound (A) can be obtained.

When the reaction between the phenol compound (a1) and the 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 convert the triarylmethane compound (A) to an aromatic Crystals of the triarylmethane type compound (A) can be precipitated by dissolving in a hydrocarbon solvent and cooling as it is.

The poor solvent (S1) used for purification of the triarylmethane compound (A) includes, for example, water; monoalcohols such as methanol, ethanol, propanol, and ethoxyethanol; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane and cyclohexane; and aromatic hydrocarbons such as toluene and xylene. These may be used independently, respectively, and may use 2 or more types together. Especially, since it is excellent in the solubility of an acid catalyst, water, methanol, and ethoxyethanol are preferable.

On the other hand, the solvent (S2), for example, monoalcohol such as methanol, ethanol, propanol; Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol polyols such as , 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, and 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, ethylene glycol ethyl methyl ether, ethylene glycol mono glycol ethers such as phenyl 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. are mentioned. These may be used independently, respectively, and may use 2 or more types together. Especially, when water or monoalcohol is used as said poor solvent (S1), it is preferable to use acetone as solvent (S2).

With respect to the phenol or phenol compound (B) having an aliphatic hydrocarbon group having 1 to 7 carbon atoms, the aliphatic hydrocarbon group having 1 to 7 carbon atoms may be either a straight chain type or a branched structure, and in the structure Either having an unsaturated group or not having an unsaturated group may be sufficient. Especially, since it becomes a phenolic hydroxyl-containing resin which is excellent in the balance of developability, heat resistance, and crack resistance, it is preferable that a phenolic compound (B) has a C1-C4 aliphatic hydrocarbon group, and it is preferable that it has a methyl group. Moreover, it is preferable that the substitution position is a meta position with respect to a phenolic hydroxyl group.

The reaction ratio between the triarylmethane type compound (A) and the phenol compound (B) is suitably changed according to the desired resin performance, use, and the like. Especially, since it becomes a phenolic hydroxyl-containing resin excellent in the balance of developability, heat resistance, and crack resistance, it is preferable that both molar ratio [(A)/(B)] is the range of 90/10-30/70, 80 It is more preferable that it is the range of /20-40/60.

The aldehyde compound (C) may be one that can undergo a condensation reaction with the triarylmethane compound (A) and the phenol compound (B) to form a novolak-type phenolic hydroxyl group-containing resin, for example, , formaldehyde, paraformaldehyde, 1,3,5-trioxane, acetaldehyde, propionaldehyde, tetraoxymethylene, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butylaldehyde, Caproaldehyde, allylaldehyde, crotonaldehyde, acrolein, etc. are mentioned. These may be used independently, respectively, and may use 2 or more types together. Among them, it is preferable to use formaldehyde because of its excellent reactivity. Formaldehyde may be used as formalin in an aqueous solution state, may be used as paraformaldehyde in a solid state, or either may be used. Moreover, when using formaldehyde and another aldehyde compound together, it is preferable to use the other aldehyde compound in the ratio of 0.05-1 mol with respect to 1 mol of formaldehyde.

The novolak resin intermediate (M) is prepared by using, as a reaction raw material, other phenolic hydroxyl group-containing compounds (E) in addition to the triarylmethane compound (A), the phenol compound (B), and the aldehyde compound (C). it may be Examples of the other phenolic hydroxyl group-containing compound (E) used herein include phenol, dihydroxybenzene, phenylphenol, bisphenol, naphthol, and dihydroxynaphthalene. These may be used independently, respectively, and may use 2 or more types together. In the case of using other phenolic hydroxyl group-containing compounds (E), the effects of the present invention are sufficiently exhibited. Therefore, in a total of 100 parts by mass of the phenolic hydroxyl group-containing compound raw materials of the novolak resin intermediate (M), the triaryl It is preferable to use 50 mass parts or more of a methane type compound (A) and a phenolic compound (B) in total, It is more preferable to use 80 mass parts or more.

The reaction molar ratio [[(A)+(B)]/(C)] of the triarylmethane type compound (A), the phenol compound (B) and the aldehyde compound (C) is excessively high ( gelation) can be suppressed and a phenolic hydroxyl group-containing resin having a suitable molecular weight as a resist composition can be obtained. desirable.

In the case of using the other phenolic hydroxyl group-containing compound (E) together, the reaction molar ratio [(P)/(C)] of the total (P) of the phenolic hydroxyl group-containing compound raw materials and the aldehyde compound (C) is , It is preferable that it is the range of 1/0.5 - 1/1.2, and it is more preferable that it is the range of 1/0.6 - 1/0.9.

The reaction of the triarylmethane compound (A), the phenol compound (B), and the aldehyde compound (C) is preferably performed under acid catalytic conditions. Examples of the acid catalyst used herein include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts may be used individually, respectively, and may use 2 or more types together. Among these, sulfuric acid and para-toluenesulfonic acid are preferable from the viewpoint of excellent catalytic activity.

You may perform reaction of the said triarylmethane type compound (A), the said phenol compound (B), and the said aldehyde compound (C) in an organic solvent as needed. The solvent used here is, for example, monoalcohol, such as methanol, ethanol, and a propanol; Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol polyols such as , 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, and 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, ethylene glycol ethyl methyl ether, ethylene glycol mono glycol ethers such as phenyl ether; cyclic ethers such as 1,3-dioxane, 1,4-dioxane, and tetrahydrofuran; glycol esters such as ethylene glycol acetate; Ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, etc. are mentioned. These solvents may be used independently, respectively, and may be used as 2 or more types of mixed solvent.

Reaction of the said triarylmethane type compound (A), the said phenol compound (B), and the said aldehyde compound (C) is carried out, for example in the temperature range of 60-140 degreeC over 0.5-20 hours.

After completion of the reaction, a novolak resin intermediate (M) can be obtained by adding water to the reaction product to perform reprecipitation operation or the like. The weight average molecular weight (Mw) of the novolac resin intermediate (M) obtained in this way is 3,000 to 50,000 because a phenolic hydroxyl group-containing resin that is excellent in the balance of developability, heat resistance and crack resistance and suitable for resist materials is obtained. range is preferred. Moreover, it is preferable that polydispersity (Mw/Mn) of phenolic hydroxyl group containing resin is the range of 3-10.

In addition, in this invention, a weight average molecular weight (Mw) and polydispersity (Mw/Mn) are values measured by GPC of the following conditions.

[Measurement conditions for GPC]

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

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

+ Showa Denko Co., Ltd. “Shodex KF803” (8.0 mmФ×300 mm) + Showa Denko Co., Ltd. “Shodex KF804” (8.0 mmФ × 300 mm)

Column temperature: 40℃

Detector: RI (Differential Refractometer)

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

Developing solvent: tetrahydrofuran

Flow rate: 1.0mL/min

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

Standard sample: the following monodisperse polystyrene

(Standard sample: monodisperse polystyrene)

"A-500" made by Tosoh Corporation

"A-2500" made by Tosoh Corporation

"A-5000" made by Tosoh Corporation

"F-1" made by Tosoh Corporation

"F-2" made by Tosoh Corporation

"F-4" made by Tosoh Corporation

"F-10" made by Tosoh Corporation

"F-20" made by Tosoh Corporation

The molecular structure of the alkene compound (D) having 8 to 24 carbon atoms is not particularly limited as long as it has an ethylenic double bond site capable of reacting with the novolak resin intermediate (M). , the following structural formula (6)

(wherein R ⁶ is an aliphatic hydrocarbon group having 6 to 22 carbon atoms)

and compounds represented by A C8-C24 alkene compound (D) may be used individually by 1 type, and may use 2 or more types together.

As long as R ⁶ in the structural formula (6) is an aliphatic hydrocarbon group having 6 to 22 carbon atoms, either a straight-chain one or a branched structure may be used, and one of those having an unsaturated group or not having an unsaturated group in the structure side may be Especially, since it becomes a phenolic hydroxyl-containing resin which is especially excellent in crack resistance, it is preferable that R< ⁶ > is a linear alkyl group, and it is especially preferable that the carbon atom number is the range of 6-18.

The reaction ratio between the novolak resin intermediate (M) and the alkene compound (D) having 8 to 24 carbon atoms gives a phenolic hydroxyl group-containing resin excellent in the balance of developability, heat resistance, and crack resistance. It is preferable that the ratio of the alkene compound (D) having 8 to 24 carbon atoms is 0.5 to 30 mass% with respect to the total mass of (M) and the alkene compound (D) having 8 to 24 carbon atoms.

The reaction between the novolak resin intermediate (M) and the alkene compound (D) having 8 to 24 carbon atoms is preferably performed under acid catalytic conditions. Examples of the acid catalyst used herein include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts may be used individually, respectively, and may use 2 or more types together. Among these, a sulfuric acid is preferable at the point which is excellent in catalytic activity.

The reaction between the novolak resin intermediate (M) and the alkene compound (D) having 8 to 24 carbon atoms may be carried out in an organic solvent if necessary. The solvent used here is, for example, monoalcohol, such as methanol, ethanol, and a propanol; Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol polyols such as , 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, and 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, ethylene glycol ethyl methyl ether, ethylene glycol mono glycol ethers such as phenyl ether; cyclic ethers such as 1,3-dioxane, 1,4-dioxane, and tetrahydrofuran; glycol esters such as ethylene glycol acetate; Ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, etc. are mentioned. These solvents may be used independently, respectively, and may be used as 2 or more types of mixed solvent.

The reaction between the novolak resin intermediate (M) and the alkene compound (D) having 8 to 24 carbon atoms is carried out, for example, in a temperature range of 60 to 140°C over 0.5 to 20 hours.

After completion of the reaction, water is added to the reaction product to perform reprecipitation operation, and the target phenolic hydroxyl group-containing resin can be obtained by washing with an appropriate organic solvent or the like. The weight average molecular weight (Mw) of the phenolic hydroxyl group-containing resin obtained in this way is excellent in the balance of developability, heat resistance and crack resistance, and is suitable for a resist material. Therefore, it is preferable that it is in the range of 3,500 to 50,000. Moreover, it is preferable that polydispersity (Mw/Mn) of phenolic hydroxyl group containing resin is the range of 3-10.

The above-described phenolic hydroxyl group-containing resin of the present invention has excellent balance of developability, heat resistance and crack resistance, and is therefore particularly useful as a resist material. It can be used for a wide variety of uses, such as various electrical/electronic member uses, such as a paint, an adhesive agent, and a printed wiring board. When the phenolic hydroxyl group-containing resin of the present invention is used for a resist material, its specific use is not particularly limited, and it can be suitably used for thick film applications, resist underlayer films, resist permanent film applications, and the like.

The photosensitive composition of this invention contains the said phenolic hydroxyl-containing resin of this invention, and a photosensitive agent as essential components. As for the said photosensitizer, the compound which has a quinonediazide group is mentioned, for example. 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 complete ester compound with the halide, a partial ester compound, an amidate, or a partially amidated compound etc. are mentioned.

The aromatic (poly)hydroxy compound is, for example, 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone , 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'-pentahydroxybenzophenone, 2,2 ',3,4,5-pentahydroxybenzophenone, 2,3',4,4',5',6-hexahydroxybenzophenone, 2,3,3',4,4',5'- polyhydroxybenzophenone compounds such as 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'-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' bis[(poly)hydroxyphenyl]alkane compounds such as -dimethyl-{1-[4-[2-(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-hydroxy hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis( Tris such as 4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane and bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane (hydroxyphenyl)methane compound or its methyl substituent;

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-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-3-hydroxy Roxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, 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) A bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methane compound, such as -2-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane, or its methyl substitution product, etc. are mentioned. These photosensitizers may be used independently, respectively, and may use 2 or more types together.

Since the compounding quantity of the said photosensitive agent in the photosensitive composition of this invention turns into the photosensitive composition excellent in photosensitivity, it is preferable that it is a ratio used as 5-50 mass parts with respect to a total of 100 mass parts of resin solid content of the photosensitive composition.

The photosensitive composition of this invention may use together other resin (X) other than phenolic hydroxyl-containing resin of the said this invention. Other resins (X) used herein include, for example, various novolac resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, and phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatics. Modified with compound Novolak resin, phenol aralkyl resin (xylok resin), naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, aminotriazine-modified A phenol resin, various vinyl polymers, etc. are mentioned.

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

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

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

In addition, when taking advantage of the excellent photosensitivity of the phenolic hydroxyl group-containing resin of the present invention and using it as a sensitivity improving agent, the phenolic hydroxyl group-containing resin of the present invention contains 3 parts by mass relative to 100 parts by mass of the other resin (X). It is preferable that it is the range of -80 mass parts.

The photosensitive composition of this invention may contain surfactant for the objective, such as the improvement of the film forming property at the time of using for a resist use, and the adhesiveness of a pattern. Surfactants used herein include, for example, polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene Polyoxyethylene alkyl allyl ether compounds such as octyl phenol ether and polyoxyethylene nonyl phenol ether, polyoxyethylene/polyoxypropylene block copolymer, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan Sorbitan fatty acid ester compounds such as bitan monooleate, sorbitan trioleate and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan monostearate Nonionic surfactants, such as polyoxyethylene sorbitan fatty acid ester compounds, such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate; a fluorine-based surfactant having a fluorine atom in its molecular structure, such as a copolymer of a polymerizable monomer having a fluoroaliphatic group and [poly(oxyalkylene)](meth)acrylate; and silicone-based surfactants having a silicone structural moiety in their molecular structure. These may be used independently, respectively, and may use 2 or more types together.

It is preferable to use the compounding quantity of these surfactant in the range of 0.001-2 mass parts with respect to a total of 100 mass parts of resin solid content in the photosensitive composition of this invention.

When the photosensitive composition of the present invention is used for a resist application, in addition to the phenolic hydroxyl group-containing resin and photosensitizer of the present invention, if necessary, other resins (X), surfactants, dyes, fillers, crosslinking agents, dissolution accelerators, etc. By adding various additives and dissolving it in an organic solvent, it can be set as a photosensitive resist material. As for the said resist material, this may be used as a porcelain as it is, and what apply|coated the resist material on the support film and desolved it may be used as a resist film. Synthetic resin films, such as polyethylene, a polypropylene, a polycarbonate, and a polyethylene terephthalate, are mentioned as a support film at the time of using as a resist film, A single|mono layer film may be sufficient, or several laminated|multilayer film may be sufficient as it. Moreover, the thing by which the corona-treated thing or the release agent was apply|coated may be sufficient as the surface of the said support film.

Although the kind of said organic solvent is not specifically limited, For example, For example, alkylene glycol monoalkyl, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether propylene glycol monomethyl ether. ether; dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; alkylene glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate; ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; cyclic ethers such as dioxane; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxy and ester compounds such as butyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate. may be used together.

The resist material of this invention can be adjusted by mix|blending each said component and mixing using a stirrer etc. In addition, when a resist material contains a filler or a pigment, it can disperse|distribute or mix and adjust using dispersing apparatuses, such as a dissolver, a homogenizer, and a three-roll mill.

In the photolithography method using the photosensitive resist material, for example, a resist material is applied onto an object to be subjected to photolithography on a silicon 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, and doctor blade coating. When the resist material of the present invention is used as a positive type, the target resist pattern is exposed through a predetermined mask, and the exposed portion is dissolved with an alkali developer to form a resist pattern. Since the resist material of the present invention has both high alkali solubility in exposed portions and high alkali solubility in non-exposed portions, it is possible to form a resist pattern having excellent resolution.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

When the curable composition of the present invention is used for a resist application, in addition to the phenolic hydroxyl group-containing resin and curing agent of the present invention, other resins (Y), surfactants, dyes, fillers, crosslinking agents, dissolution accelerators, etc., if necessary By adding various additives and dissolving in an organic solvent, it can be set as a curable resist material.

Although the kind of said organic solvent is not specifically limited, For example, For example, alkylene glycol monoalkyl, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether propylene glycol monomethyl ether. ether; dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; alkylene glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate; ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; cyclic ethers such as dioxane; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxy and ester compounds such as butyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate. may be used together.

The said resist material can be adjusted by mix|blending each said component and mixing using a stirrer etc. In addition, when a resist material contains a filler or a pigment, it can disperse|distribute or mix and adjust using dispersing apparatuses, such as a dissolver, a homogenizer, and a three-roll mill.

A curable resist material can be used especially suitably for a resist underlayer film use. In order to produce a resist underlayer film from the resist material, for example, the resist material is applied onto an object to be subjected to photolithography such as a silicon substrate, dried under a temperature condition of 100 to 200° C., and then further 250 to 400° C. A resist underlayer film is formed by a method such as heat curing under a temperature condition of Next, a resist pattern is formed by performing a normal photolithography operation on this underlayer film, and dry etching treatment is performed with a halogen-based plasma gas or the like, whereby a resist pattern by the multilayer resist method can be formed.

(Example)

Hereinafter, the present invention will be described in more detail by giving specific examples. In addition, the number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity (Mw/Mn) of synthesize|combined resin are measured on the measurement conditions of the following GPC.

[Measurement conditions for GPC]

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

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

+ Showa Denko Co., Ltd. “Shodex KF803” (8.0 mmФ×300 mm) + Showa Denko Co., Ltd. “Shodex KF804” (8.0 mmФ × 300 mm)

Column temperature: 40℃

Detector: RI (Differential Refractometer)

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

Developing solvent: tetrahydrofuran

Flow rate: 1.0mL/min

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

Injection volume: 0.1mL

Standard sample: the following monodisperse polystyrene

(Standard sample: monodisperse polystyrene)

"A-500" made by Tosoh Corporation

"A-2500" made by Tosoh Corporation

"A-5000" made by Tosoh Corporation

"F-1" made by Tosoh Corporation

"F-2" made by Tosoh Corporation

"F-4" made by Tosoh Corporation

"F-10" made by Tosoh Corporation

"F-20" made by Tosoh Corporation

In addition, the measurement of the ¹³ C-NMR spectrum analyzed the DMSO-d ₆ solution of the sample using "AL-400" manufactured by Nippon Electronics Co., Ltd., and performed structural analysis. Below, the measurement conditions of ¹³ C-NMR spectrum are shown.

[ ¹³ C-NMR spectrum measurement conditions]

Measurement mode: SGNNE (1H complete decoupling method of NOE cancellation)

Pulse angle: 45℃ pulse

Sample concentration: 30wt%

Integration count: 10000 times

Preparation Example 1 Preparation of triarylmethane compound (A-1)

In a 3000 ml four-necked flask equipped with a cooling tube, 586.4 g of 2,5-xylenol and 244 g of 4-hydroxybenzaldehyde were added and dissolved in 1000 ml of 2-ethoxyethanol. After adding 30 ml of sulfuric acid while cooling in an ice bath, it heated to 100 degreeC with a mantle heater, and made it react, stirring for 2 hours. After completion of the reaction, water was added to the obtained solution to reprecipitate the crude product. The crude product was redissolved in acetone and further reprecipitated with water, and then the precipitate was filtered off and dried in vacuo to obtain 421 g of a white crystal triarylmethane compound (A-1). ¹³ C-NMR confirmed the formation of a compound represented by the following structural formula. The purity calculated from the GPC chart was 98.2% of the GPC purity. The GPC chart of the triarylmethane type compound (A-1) is shown in FIG. 1, and the ¹³ C-NMR chart is shown in FIG.

Preparation Example 2 Preparation of novolak resin intermediate (M-1)

174 g of triarylmethane compound (A-1) and 54 g of m-cresol were put into a 3000 ml four-neck flask equipped with a cooling tube, and then dissolved in 500 ml of 2-ethoxyethanol and 500 ml of acetic acid. After 50 ml of sulfuric acid was added while cooling in an ice bath, 33 g of 92% paraformaldehyde was added. It was heated to 80 degreeC in an oil bath, and it was made to react while stirring for 10 hours. After completion of the reaction, water was added to the obtained solution to reprecipitate the crude product. The crude product was redissolved in acetone and further reprecipitated with water, the precipitate was filtered off and dried under vacuum to obtain 213 g of a red powdery novolak resin intermediate (M-1). The number average molecular weight (Mn) of the novolak resin intermediate (M-1) was 1,937, the weight average molecular weight (Mw) was 12,822, and the polydispersity (Mw/Mn) was 6.62.

Preparation Example 3 Preparation of novolak resin intermediate (M-2)

249 g of triarylmethane compound (A-1) and 31 g of m-cresol were added to a 3000 ml four-neck flask equipped with a cooling tube, and then dissolved in 500 ml of 2-ethoxyethanol and 500 ml of acetic acid. After 50 ml of sulfuric acid was added while cooling in an ice bath, 33 g of 92% paraformaldehyde was added. It was heated to 80 degreeC in an oil bath, and it was made to react while stirring for 10 hours. After completion of the reaction, water was added to the obtained solution to reprecipitate the crude product. The crude product was re-dissolved in acetone and further reprecipitated with water, the precipitate was filtered off and dried under vacuum to obtain 266 g of a red powdery novolak resin intermediate (M-2). The number average molecular weight (Mn) of the novolak resin intermediate (M-2) was 2,018, the weight average molecular weight (Mw) was 11,486, and the polydispersity (Mw/Mn) was 5.69.

Preparation Example 4 Preparation of novolak resin intermediate (M-3)

174 g of triarylmethane compound (A-1) and 54 g of m-cresol were put into a 3000 ml four-neck flask equipped with a cooling tube, and then dissolved in 500 ml of 2-ethoxyethanol and 500 ml of acetic acid. After 50 ml of sulfuric acid was added while cooling in an ice bath, 30 g of 92% paraformaldehyde was added. It was heated to 80° C. in an oil bath, and reacted with stirring for 8 hours. After completion of the reaction, water was added to the obtained solution to reprecipitate the crude product. The crude product was re-dissolved in acetone and further reprecipitated with water, the precipitate was filtered off and dried under vacuum to obtain 218 g of a red powdery novolak resin intermediate (M-3). The number average molecular weight (Mn) of the novolak resin intermediate (M-3) was 1,538, the weight average molecular weight (Mw) was 6,508, and the polydispersity (Mw/Mn) was 4.23.

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

30 g of novolak resin intermediate (M-1) and 3.0 g of 1-octene were added to a 300 ml 4-neck flask equipped with a cooling tube, and then dissolved in 100 ml of 2-ethoxyethanol. After adding 10 ml of sulfuric acid while cooling in an ice bath, it was heated to 80° C. in an oil bath, and reacted with stirring for 6 hours. After completion of the reaction, water was added to the obtained solution to reprecipitate the crude product. Next, after dissolving a crude product in methanol, hexane was added and re-precipitation was carried out, the precipitate was filtered off and vacuum-dried, 29 g of red powder phenolic hydroxyl-containing resin (1) was obtained. The number average molecular weight (Mn) of phenolic hydroxyl group containing resin (1) was 1,827, the weight average molecular weight (Mw) was 12,209, and the polydispersity (Mw/Mn) was 6.68. The GPC chart of phenolic hydroxyl group containing resin (1) is shown in FIG.

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

Except having changed 3.0 g of 1-octene into 1.5 g of 1-octadecene, operation similar to Example 1 was performed, and 27 g of red powder phenolic hydroxyl-containing resin (2) was obtained. The number average molecular weight (Mn) of phenolic hydroxyl group containing resin (2) was 1,860, the weight average molecular weight (Mw) was 13,740, and the polydispersity (Mw/Mn) was 7.39. The GPC chart of phenolic hydroxyl group containing resin (2) is shown in FIG.

Example 3 Preparation of phenolic hydroxyl group-containing resin (3)

The same procedure as in Example 1 was followed except that 30 g of the novolac resin intermediate (M-1) was changed to 30 g of the novolak resin intermediate (M-2), and 3.0 g of 1-octene was changed to 3.0 g of 1-dodecene. It carried out and obtained 30 g of red powder phenolic hydroxyl-containing resin (3). The number average molecular weight (Mn) of phenolic hydroxyl group containing resin (3) was 10,756, the weight average molecular weight (Mw) of 2010, and the polydispersity (Mw/Mn) was 5.35. The GPC chart of phenolic hydroxyl group containing resin (3) is shown in FIG.

Example 4 Preparation of phenolic hydroxyl group-containing resin (4)

The same procedure as in Example 1 was followed except that 30 g of the novolac resin intermediate (M-1) was changed to 30 g of the novolak resin intermediate (M-3), and 3.0 g of 1-octene was changed to 1.5 g of 1-dodecene. and 28 g of red powder phenolic hydroxyl group-containing resin (4) was obtained. The number average molecular weight (Mn) of phenolic hydroxyl group containing resin (4) was 1,572, the weight average molecular weight (Mw) was 6,784, and the polydispersity (Mw/Mn) was 4.32. The GPC chart of phenolic hydroxyl group containing resin (4) is shown in FIG.

Example 5 Preparation of phenolic hydroxyl group-containing resin (5)

30 g of the novolac resin intermediate (M-1) was changed to 30 g of the novolak resin intermediate (M-3), and 3.0 g of 1-octene was replaced with "Linearen 148" manufactured by Idemitsu Kosan Co., Ltd. [1-tetradecene, 1 -35:37:28 (molar ratio) mixture of hexadecene and 1-octadecene] Except having changed to 1.5 g, operation similar to Example 1 was performed, and 29 g of red powder phenolic hydroxyl-containing resin (5) was obtained. . The number average molecular weight (Mn) of phenolic hydroxyl group containing resin (5) was 1,586, the weight average molecular weight (Mw) was 6,829, and the polydispersity (Mw/Mn) was 4.31. The GPC chart of phenolic hydroxyl group containing resin (4) is shown in FIG.

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

In a 2L 4-neck 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 put, and the mixture was heated to 100° C. and reacted. Dehydration and distillation were carried out by heating from normal pressure to 200°C, and further distillation 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 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.

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

13.0 g of methacresol, 8.6 g of paracresol, and 6.1 g of 3-pentadecylphenol were put into a 300 ml 4-neck flask equipped with a cooling tube, and then dissolved in 15 ml of 2-ethoxyethanol and 15 ml of acetic acid. After 10 ml of sulfuric acid was added while cooling in an ice bath, 6.5 g of 92% paraformaldehyde was added. It was heated to 80 degreeC in an oil bath, and it was made to react while stirring for 10 hours. After completion of the reaction, water was added to the obtained solution to reprecipitate the crude product. The crude product was re-dissolved in acetone and further reprecipitated with water, and then the precipitate was filtered off and dried under vacuum to obtain 24.6 g of a yellow powdery phenolic hydroxyl group-containing resin (2'). The number average molecular weight (Mn) of the phenolic hydroxyl group-containing resin (2') was 1,792, the weight average molecular weight (Mw) was 11,701, and the polydispersity (Mw/Mn) was 6.53.

Examples 6 to 10 and Comparative Examples 1 and 2

The phenolic hydroxyl group-containing resins obtained in Examples 1 to 5 and Comparative Production Examples 1 and 2 were evaluated in the following manner. A result is shown in Table 1.

Adjustment of the photosensitive composition

28 mass parts of said phenolic hydroxyl-containing resin was melt|dissolved in 60 mass parts of propylene glycol monomethyl ether acetate, and 12 mass parts of photosensitizers were added and dissolved in this solution. This was filtered with a 0.2-micrometer membrane filter, and the photosensitive composition was obtained.

Photosensitizer "P-200" manufactured by Toyo Gosei Kogyo Co., Ltd. (4,4'-[1-[4-[1-(4-hydroxyphenyl)-1 methylethyl]phenyl]ethylidene]bisphenol 1 mole and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (condensate of 2 moles) were used.

Adjustment of composition for heat resistance test

28 parts by mass of the phenolic hydroxyl group-containing resin was dissolved in 60 parts by mass of propylene glycol monomethyl ether acetate, and this was filtered through a 0.2 µm membrane filter to obtain a composition for a heat resistance test.

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

The photosensitive composition obtained above was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 μm, and dried for 60 seconds on a hot plate at 110°C. Two of these wafers were prepared, and one of them was used as a "sample without exposure". Using the other side as the "exposed sample", irradiating 100 mJ/cm2 of ghi radiation using a ghi-ray lamp ("Multilight" manufactured by Ushio Denki Co., Ltd.), heat treatment at 140°C for 60 seconds. did

Both the "sample without exposure" and the "sample with exposure" were immersed in an alkaline developer (2.38% aqueous tetramethylammonium hydroxide 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 a developer was measured, and the value obtained by dividing the difference by 60 was defined as alkali developability [ADR (Å/s)].

Evaluation of photosensitivity

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

The exposure dose (Eop dose) capable of faithfully reproducing a line width of 3 µm when the ghi line exposure dose was increased from 30 mJ/cm 2 to every 10 mJ/cm 2 was evaluated.

evaluation of resolution

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

Heat resistance evaluation

The above-obtained composition for heat resistance test was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 μm, and dried on a hot plate at 110° C. for 60 seconds. The resin component was scraped off 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) under nitrogen atmosphere, in a temperature range of -100 to 250° C., under conditions of a temperature increase of 10° C./min. was done in

Evaluation of crack resistance

The photosensitive composition obtained above was applied on a 5-inch silicon wafer by a spin coater, and dried for 300 seconds on a hot plate at 110°C. This coating operation was repeated, and the wafer whose coating film thickness is 50 micrometers and the wafer whose coating film thickness is 100 micrometers was produced. The surface of the wafer was observed using a laser microscope ("VK-X200" manufactured by Co., Ltd.), and the case where there was no crack was evaluated as (circle), and the case where there was a crack was evaluated as x.

evaluation of flexibility

The photosensitive composition obtained above was applied on a polyimide film having a thickness of 50 μm with a spin coater to a thickness of about 5 μm, and dried on a hot plate at 110° C. for 300 seconds. The obtained laminated film was bent at 180 degrees, and the state of the bent location was observed using a laser microscope ("VK-X200" manufactured by Co., Ltd.), and the case without cracks was evaluated as ○, and the case with cracks was evaluated as x. did.

[Table 1]

Examples 11 to 15 and Comparative Examples 3 and 4

The phenolic hydroxyl group-containing resins obtained in Examples 1 to 5 and Comparative Production Examples 1 and 2 were evaluated in the following manner. A result is shown in Table 2.

Adjustment of the curable composition

16 parts by mass of the phenolic hydroxyl group-containing resin, 4 parts by mass of a curing agent (“1,3,4,6-tetrakis(methoxymethyl)glycoluril” manufactured by Tokyo Chemical Industry Co., Ltd.) propylene glycol monomethyl ether acetate It melt|dissolved in 30 mass parts, this was filtered with a 0.2-micrometer membrane filter, and the curable composition was obtained.

Evaluation of alkali developability [ADR(Å/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 mu m, and dried on a hot plate at 110 DEG C for 60 seconds. Two of these wafers were prepared, and one of them was used as an "uncured sample". The other was made into a "cured sample" and heat-processed on 160 degreeC and conditions for 60 second.

Both the "uncured sample" and the "cured sample" were 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 of each sample before and after immersion in a developer was measured, and the value obtained by dividing the difference by 60 was defined as alkali developability [ADR (Å/s)].

Heat resistance evaluation

The curable composition obtained above was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 µm, dried on a hot plate at 110°C for 60 seconds, and then heat-treated at 160°C for 60 seconds. The resin component was scraped off 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.), in a nitrogen atmosphere, in a temperature range of -100 to 250° C., under conditions of a temperature increase of 10° C./min. was done in

crack resistance

The curable composition obtained above was applied on a 5-inch silicon wafer with a spin coater, and dried for 300 seconds on a hot plate at 110°C. This coating operation was repeated, and the wafer whose thickness of a coating film is 50 micrometers and the wafer whose thickness of a coating film is 100 micrometers was produced. The surface of the wafer was observed using a laser microscope ("VK-X200" manufactured by Co., Ltd.), and the case where there was no crack was evaluated as (circle), and the case where there was a crack was evaluated as x.

[Table 2]

Claims (9)

The following structural formula (1) or (2)

[In the formula, R ¹ is any one of a hydrogen atom, an aliphatic hydrocarbon group, and an aromatic ring-containing hydrocarbon group. k is any one of 0, 1, or 2. R ² and R ³ are each independently any one of an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, and a halogen atom, l is each independently 0 or an integer of 1 to 4, m is 0 or 1 to 5 An integer, n is 0 or an integer of 1-7. * is a point of bonding with the illustrated benzene ring or naphthalene ring, and both * may be bonded to the same aromatic ring or may be bonded to different aromatic rings]
The structural moiety (α) represented by and the following structural formula (3)

(Wherein, R ¹ is any one of a hydrogen atom, an aliphatic hydrocarbon group, and an aromatic ring-containing hydrocarbon group. R ⁴ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 7 carbon atoms. R ⁵ is a hydrogen atom or an aliphatic hydrocarbon group having 8 carbon atoms. -24 is an aliphatic hydrocarbon group)
^{A phenolic} hydroxyl group ^- containing resin having a structural moiety (β) represented by A resist material comprising. According to claim 1,
The resist material in the phenolic hydroxyl group-containing resin, wherein the abundance ratio [(α)/(β)] of the structural moiety (α) to the structural moiety (β) is in the range of 90/10 to 30/70. The following structural formula (4) or (5)

[In the formula, k is any one of 0, 1, and 2. R ² and R ³ are each independently any one of an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, and a halogen atom, l is each independently 0 or an integer of 1 to 4, m is 0 or 1 to 5 An integer, n is 0 or an integer of 1-7]
A novolak resin intermediate using a triarylmethane compound (A) having a molecular structure represented by , a phenol compound (B) having a phenol or aliphatic hydrocarbon group having 1 to 7 carbon atoms, and an aldehyde compound (C) as reaction raw materials A resist material comprising (M) and a phenolic hydroxyl group-containing resin which is a reaction product of an alkene compound (D) having 8 to 24 carbon atoms. 4. The method of claim 3,
The reaction ratio of the novolak resin intermediate (M) and the alkene compound (D) having 8 to 24 carbon atoms is 0.5 to the alkene compound (D) having 8 to 24 carbon atoms with respect to the total mass of both. A resist material in a proportion of 30% by mass. 5. The method according to any one of claims 1 to 4,
A resist material further containing a photosensitizer. delete 5. The method according to any one of claims 1 to 4,
A resist material further containing a curing agent. delete delete

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