TW201827478A - Phenolic hydroxyl group-containing resin and resist material - Google Patents

Abstract

The purpose of the invention is to provide: a phenolic hydroxyl group-containing resin having excellent heat resistance and alkali developability, and also having excellent crack resistance when formed into a thick film; and a photosensitive composition, a curable composition, and a resist material containing said resin. Provided is a phenolic hydroxyl group-containing resin comprising, as repeating units, a structural section ([alpha]) represented by structural formula (1) or (2) (wherein R2 and R3 each independently represent an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, or a halogen atom) and a structural section ([beta]) represented by structural formula (3) (wherein R4 is a hydrogen atom or a C1-7 aliphatic hydrocarbon group, and R5 is a hydrogen atom or a C8-24 aliphatic hydrocarbon group), the phenolic hydroxyl group-containing resin being characterized in that at least one of R2, R3 and R5 present in the resin is a C8-24 aliphatic hydrocarbon group.

Description

 Phenolic hydroxyl-containing resin and resist material  

The present invention relates to a phenolic hydroxyl group-containing resin which is excellent in heat resistance and alkali developability, and which is excellent in crack resistance when a thick film is formed, a photosensitive composition containing the same, a curable composition, and a resist. material.

In the field of photoresists, various resist pattern forming methods which are subdivided according to the use or function have been developed, and the required performance of the resin material for resists has been increased and diversified. For example, in the resin material for pattern formation, high developability for forming a fine pattern accurately and with high productivity in a highly integrated semiconductor is required. In applications called base films, antireflective films, BARC films, hard masks, etc., dry etching resistance or low reflectivity is required, and it is required to form tens of micrometers thick in the foremost field. The film does not cause cracks or cracks. Further, in applications called a resist permanent film or the like, in addition to high heat resistance, it is required to form a thick film without causing deterioration over time. Further, from the viewpoint of quality reliability, long-term storage stability in various environments in various countries of the world is also one of important performances.

The phenolic phenol-containing resin cresol novolak type most widely used in photoresist applications, but it is not suitable for the recent market-required performance of high-grade and diversified development, and heat resistance or developability is insufficient. Further, if a thick film is formed, cracking occurs, so that it is not suitable for a thick film application (see Patent Document 1).

[Previous Technical Literature]

[Patent Literature]

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

Therefore, 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, and excellent in crack resistance at the time of formation of a thick film, a photosensitive composition containing the same, and curability. Composition, and resist material.

The present inventors have made an effort to solve the above problems, and have found that an olefin compound having 8 to 24 carbon atoms and a phenolic hydroxyl group-containing compound having a triarylmethane type have a phenol or a fat having 1 to 7 carbon atoms. The phenolic hydroxyl group-containing resin obtained by reacting a phenolic compound having a phenolic compound as a reaction raw material is excellent in heat resistance and alkali developability, and is excellent in crack resistance when a thick film is formed, thereby completing the present invention. invention.

In other words, the present invention relates to a phenolic hydroxyl group-containing resin which has a structural moiety (α) represented by the following structural formula (1) or (2) and is represented by the following structural formula (3). The structural part (β) is 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.

(wherein 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, and 2. R ² and R ³ are each independently an aliphatic hydrocarbon group, and Any one of a hydrocarbon group, an alkoxy group and a halogen atom of the aromatic ring, l is independently an integer of 0 or 1 to 4, m is an integer of 0 or 1 to 5, and n is an integer of 0 or 1 to 7. For the bond to the benzene ring or naphthalene ring shown in the figure, the two * may also be bonded to the same aromatic ring or may be bonded to a different aromatic ring)

(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; and R ⁵ is a hydrogen atom or a carbon atom; 8~24 aliphatic hydrocarbon group)

The present invention further relates to a phenolic hydroxyl group-containing resin which is a reactant of a novolak resin intermediate (M) and an olefin compound (D) having 8 to 24 carbon atoms; the novolac resin intermediate (M) a triarylmethane type compound (A) having a molecular structure represented by the following structural formula (4) or (5), a phenol compound (B) having a phenol or an aliphatic hydrocarbon group having 1 to 7 carbon atoms, And an aldehyde compound (C) as a reaction raw material.

(wherein k is any one of 0, 1, and 2. R ² and R ³ are each independently an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, or a halogen atom, and each independently Is an integer of 0 or 1~4, m is an integer of 0 or 1~5, n is an integer of 0 or 1~7)

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

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

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

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

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

According to the present invention, it is possible to provide a phenolic hydroxyl group-containing resin excellent in heat resistance and alkali developability, and excellent in crack resistance in forming a thick film, a photosensitive composition containing the same, a curable composition, and an anti-resistance. Etch material.

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

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

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

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

Fig. 5 is a GPC chart of the phenolic hydroxyl group-containing resin (3) obtained in Example 3.

Fig. 6 is a GPC line diagram of the phenolic hydroxyl group-containing resin (4) obtained in Example 4.

Fig. 7 is a GPC line diagram of the 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 is characterized by having a structural moiety (α) represented by the following structural formula (1) or (2) and a structural moiety (β) represented by the following structural formula (3); As the repeating unit, 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.

(wherein 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, and 2. R ² and R ³ are each independently an aliphatic hydrocarbon group, and Any one of a hydrocarbon group, an alkoxy group and a halogen atom of the aromatic ring, l is independently an integer of 0 or 1 to 4, m is an integer of 0 or 1 to 5, and n is an integer of 0 or 1 to 7. For the bond to the benzene ring or naphthalene ring shown in the figure, the two * may also be bonded to the same aromatic ring or may be bonded to a different aromatic ring)

(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; and R ⁵ is a hydrogen atom or a carbon atom; 8~24 aliphatic hydrocarbon group)

The phenolic hydroxyl group-containing resin of the present invention has a high symmetry and a rigid structural unit (α) as a repeating unit and has a phenolic hydroxyl group at a high density, so that it has high heat resistance and excellent developability. The present invention is designed not only by the above-mentioned structural part (α) but also by the above-mentioned structural part (β) as a repeating unit resin, and by introducing an aliphatic hydrocarbon group having 8 to 24 carbon atoms into the resin structure, thereby maintaining In the case of heat resistance and developability, the crack resistance at the time of forming a thick film is also improved. In general, a method of introducing a long-chain aliphatic hydrocarbon group or the like into a resin structure to improve the flexibility or toughness of the resin has an effect of improving crack resistance, but is often accompanied by a decrease in functional group density. In the present invention, it is a resin containing a phenolic hydroxyl group which is excellent in any of developability, heat resistance, and crack resistance without lowering the developability and the heat resistance.

R ¹ in the above structural formulae (1), (2), and (3) is any ^one of a hydrogen atom, an aliphatic hydrocarbon group, and a hydrocarbon group containing an aromatic ring. Examples of the aliphatic hydrocarbon group include a carbon such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group or a decyl group. The number of atoms is 1 to 9 alkyl groups and the like. Examples of the aromatic ring-containing hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a fluorenyl group, and a structural moiety substituted with an alkyl group, an alkoxy group, a halogen atom or the like on the aromatic nucleus. In the phenolic hydroxyl group-containing resin which is excellent in balance between developability, heat resistance and crack resistance, R ^{1 is} preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom. .

With respect to the above-mentioned structural portion (α), * in the above structural formulae (1) and (2) is a bonding point with any one of the three aromatic rings illustrated in the above structural formulas (1) and (2). , 2 * can be bonded to the same aromatic ring, or can be bonded to different aromatic rings. Specific examples of the structural positions represented by the above structural formula (1) include those represented by any one of the following structural formulae (1-1) to (1-4). Further, the structural portion represented by the above structural formula (2) is specifically represented by any one of the following structural formulae (2-1) to (2-4).

(wherein 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, and 2. R ² and R ³ are each independently an aliphatic hydrocarbon group, and Any one of a hydrocarbon group, an alkoxy group and a halogen atom of an aromatic ring, each independently being an integer of 0 or 1 to 4, and m is an integer of 0 or 1 to 5)

(wherein 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, and ^2. R ² and R ³ are each independently an aliphatic hydrocarbon group, and Any one of a hydrocarbon group, an alkoxy group and a halogen atom of an aromatic ring, each independently being an integer of 0 or 1 to 4, and n is an integer of 0 or 1 to 7)

Regarding the phenolic hydroxyl group-containing resin of the present invention, all the structural sites (α) present in the resin may have the same structure or may have various structures. Among them, the phenolic hydroxyl group-containing resin which is excellent in balance between developability, heat resistance and crack resistance preferably has a structural portion represented by the above structural formula (1). Further, it is preferable that the value of k in the above structural formulae (1) and (2) is 1. When the value of k is 1, the bonding position of the three phenolic hydroxyl groups in the above structural formula (1) is preferably aligned with respect to the methine groups of the three aromatic rings bonded to each other.

R ² in the above structural formulae (1) and (2) are each independently an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, or a halogen atom, and l is independently 0 or 1 to 4, respectively. Integer. The aliphatic hydrocarbon group may be either a linear one or a branched structure, or may be one having an unsaturated group in the structure and not having an unsaturated group. The number of carbon atoms is not particularly limited, and may be any one of a short chain having 1 to 6 carbon atoms or a relatively long chain having 7 or more carbon atoms. The specific structure of the aromatic ring-containing hydrocarbon group is not particularly limited as long as it is a structural portion containing an aromatic ring, and examples of the aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group or a fluorenyl group include a benzyl group. An aralkyl group such as phenylethyl, phenylpropyl or naphthylmethyl. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and a cyclohexyloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

Among them, in the case of a phenolic hydroxyl group-containing resin excellent in balance between developability, heat resistance and crack resistance, 1 is preferably an integer of 2 to 4, and two R ² are 1 to 3 carbon atoms. The alkyl group, and the other R ² is a hydrogen atom or an aliphatic hydrocarbon group having 8 to 24 carbon atoms. Further, two R ² of an alkyl group having 1 to 3 carbon atoms are preferably bonded to the 2,5-position of the phenolic hydroxyl group.

R ³ in the above structural formulae (1) and (2) are 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 an integer of 0 or 1~7. The aliphatic hydrocarbon group may be either a linear one or a branched structure, or may be one having an unsaturated group in the structure and not having an unsaturated group. The number of carbon atoms is not particularly limited, and may be any one of a short chain having 1 to 6 carbon atoms or a relatively long chain having 7 or more carbon atoms. The specific structure of the aromatic ring-containing hydrocarbon group is not particularly limited as long as it is a structural portion containing an aromatic ring, and examples of the aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group or a fluorenyl group include a benzyl group. An aralkyl group such as phenylethyl, phenylpropyl or naphthylmethyl. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and a cyclohexyloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. In particular, R ^{3 is} preferably a hydrogen atom or an aliphatic hydrocarbon group having 9 to 24 carbon atoms, which is a phenolic hydroxyl group-containing resin excellent in balance between developability, heat resistance and crack resistance.

In the above structural moiety (β), R ⁴ in the above 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. The aliphatic hydrocarbon group may be either a linear type or a branched structure, or may be one having an unsaturated group in the structure and having no unsaturated group, or may have a structure Any of those that are not saturated and have no unsaturated groups. . In particular, R ^{4 is} preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and preferably a methyl group, in terms of a phenolic hydroxyl group-containing resin having excellent balance between developability, heat resistance and crack resistance. Further, the substitution position is preferably a meta position for the phenolic hydroxyl group.

In the phenolic hydroxyl group-containing resin of the present invention, the ratio of the above-mentioned structural portion (α) to the above-mentioned structural portion (β) is appropriately changed depending on the desired resin properties, use, and the like. Among them, the resin having a phenolic hydroxyl group which is excellent in balance between developability, heat resistance and crack resistance is preferably present in a ratio of [(α)/(β)] of 90/10 to 30/ The range of 70 is more preferably in the range of 80/20 to 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 linear type or a branched structure, or may be one having an unsaturated group in the structure and having no unsaturated group, or may be Any of those having an unsaturated group and no unsaturated group in the structure. In particular, the phenolic hydroxyl group-containing resin which is excellent in balance between developability, heat resistance and crack resistance is preferably an aliphatic hydrocarbon group having 8 to 20 carbon atoms. Further, it is preferably an alkyl group whose structure is a linear type.

In the phenolic hydroxyl group-containing resin which is excellent in balance between developability, heat resistance and crack resistance, the aliphatic hydrocarbon group having 8 to 24 carbon atoms is preferably present in a proportion of 100 parts by mass of the phenolic hydroxyl group-containing resin. In the above, the aliphatic hydrocarbon group having 8 to 24 carbon atoms is in a ratio of 0.5 to 30% by mass.

The method for producing the phenolic hydroxyl group-containing resin of the present invention is not particularly limited, and it can be produced, for example, by the following method: a novolak resin intermediate (M) and an olefin compound having 8 to 24 carbon atoms ( D) The reaction is carried out, and the novolac resin intermediate (M) is a triarylmethane type compound (A) having a molecular structure represented by the following structural formula (4) or (5), having a phenol or a carbon number of 1 The phenolic compound (B) of the aliphatic hydrocarbon group of ~7 and the aldehyde compound (C) are used as a reaction raw material.

(wherein k is any of 0, 1, and 2. R ² and R ³ are each independently an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, or a halogen atom, and each independently Is an integer of 0 or 1~4, m is an integer of 0 or 1~5, n is an integer of 0 or 1~7)

The above triarylmethane type compound (A) may be used alone or in combination of a plurality of compounds having different molecular structures. In particular, the phenolic hydroxyl group-containing resin which is excellent in balance between developability, heat resistance and crack resistance is preferably one having the molecular structure represented by the above structural formula (4). Further, it is preferable that the value of k is 1. In the case where the value of k is 1, in the structural formula (4), the bonding position of the three phenolic hydroxyl groups in the molecular structure is preferably a para position relative to the methine group of the three aromatic rings bonded.

The triarylmethane type compound (A) is, for example, obtained by a condensation reaction of a phenol compound (a1) and an aromatic aldehyde compound (a2). The phenol compound (a1) may, for example, be a compound in which one or more hydrogen atoms on the aromatic nucleus of the phenol are substituted with an alkyl group, an alkoxy group, a halogen atom or the like. These may be used alone or in combination of two or more. Among them, a resin having a phenolic hydroxyl group which is excellent in heat resistance is preferably an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group or a halogen atom at the 2,5-position of the phenol. The compound is preferably a compound having an alkyl group having 1 to 3 carbon atoms at the 2,5-position, and particularly preferably 2,5-xylenol.

The aromatic aldehyde compound (a2) may, for example, be a compound having a fluorenyl group on an aromatic nucleus such as benzene, naphthalene, phenol, resorcin, naphthol or dihydroxynaphthalene, or an alkyl group in addition to a formazan group. A compound such as an alkoxy group or a halogen atom. These may be used alone or in combination of two or more. Among them, a resin having a phenolic hydroxyl group which is excellent in balance between heat resistance and developability is preferably a benzene ring structure, and specifically, benzaldehyde, salicylaldehyde, m-hydroxybenzaldehyde, and preferably Hydroxybenzaldehyde is more preferably salicylaldehyde, m-hydroxybenzaldehyde or p-hydroxybenzaldehyde.

The molar ratio [(a)/(b)] of the above phenol compound (a1) to the aromatic aldehyde compound (a2) is higher than that of the triarylmethane type compound (A) obtained in high yield and high purity. Preferably, it is 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 of the phenol compound (a1) with the aromatic aldehyde compound (a2) is preferably carried out under acid catalyst conditions. Examples of the acid catalyst used herein include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts may be used singly or in combination of two or more. Among these, sulfuric acid and p-toluenesulfonic acid are preferred in terms of excellent catalyst activity.

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

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

After completion of the reaction, for example, by introducing the reaction product into the poor solvent (S1) of the triarylmethane type compound (A) and filtering the precipitate, the solubility of the triarylmethane type compound (A) is high and The method of re-dissolving the precipitate obtained in the solvent (S2) in which the poor solvent (S1) is mixed, removes the unreacted phenol compound (a1) or the aromatic aldehyde compound (a2) from the reaction product, and uses the acid touch The medium is obtained to obtain a purified triarylmethane type compound (A).

When the reaction of the phenol compound (a1) with 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 cause the above triarylmethane type compound (A). The crystal of the above triarylmethane type compound (A) is precipitated by dissolving in an aromatic hydrocarbon solvent and directly cooling it.

The poor solvent (S1) used for the purification of the above triarylmethane type compound (A) may, for example, be water; a monoalcohol such as methanol, ethanol, propanol or ethoxyethanol; n-hexane, n-heptane or n-octane An aliphatic hydrocarbon such as an alkane or a cyclohexane; or an aromatic hydrocarbon such as toluene or xylene. These may be used alone or in combination of two or more. Among them, water, methanol, and ethoxyethanol are preferred in terms of excellent solubility of the acid catalyst.

On the other hand, examples of the solvent (S2) include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and 1,5. - pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene Polyols such as diol and glycerin; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, and B Glycol ethers such as glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether; cyclic ethers such as 1,3-dioxane and 1,4-dioxane; ethylene glycol acetate, etc. a glycol ester; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone. These may be used alone or in combination of two or more. In the case where water or a monol is used as the poor solvent (S1), acetone is preferably used as the solvent (S2).

The above phenol compound (B) having a phenol or an aliphatic hydrocarbon group having 1 to 7 carbon atoms, and an aliphatic hydrocarbon group having 1 to 7 carbon atoms may be a linear one or a branched structure. Any one of those having an unsaturated group in the structure and having no unsaturated group may be any one having an unsaturated group in the structure and not having an unsaturated group. In particular, the phenolic compound having a phenolic hydroxyl group which is excellent in balance between developability, heat resistance and crack resistance is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, preferably Has a methyl group. Further, the substitution position is preferably a meta position relative to the phenolic hydroxyl group.

The reaction ratio of the above triarylmethane type compound (A) to the above phenol compound (B) is appropriately changed depending on the desired resin properties, use, and the like. Among them, in the case of a phenolic hydroxyl group-containing resin excellent in balance between developability, heat resistance and crack resistance, it is preferred that the molar ratio [(A)/(B)] of both is 90/10~ The range of 30/70 is more preferably in the range of 80/20 to 40/60.

The aldehyde compound (C) may be a phenolic phenol-containing resin which forms a novolak type condensate reaction with the triarylmethane type compound (A) and the phenol compound (B), and examples thereof include formaldehyde. , polyoxymethylene, 1,3,5-trioxane, acetaldehyde, propionaldehyde, tetraformaldehyde, polyoxymethylene, trichloroacetaldehyde, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, hexanal, Allyl aldehyde, crotonaldehyde, acrolein, and the like. These may be used alone or in combination of two or more. Among them, in terms of excellent reactivity, it is preferred to use formaldehyde. Formaldehyde can be used in the form of a form of an aqueous solution in the form of a solution, or it can be used in the form of a form of paraformaldehyde in a solid state. Further, in the case where formaldehyde and other aldehyde compounds are used in combination, it is preferred to use other aldehyde compounds in a ratio of 0.05 to 1 mol with respect to formaldehyde 1 mol.

In addition to the above triarylmethane type compound (A), the above phenol compound (B) and the above aldehyde compound (C), the above-mentioned novolak resin intermediate (M) may be reacted with other phenolic hydroxyl group-containing compound (E). raw material. Examples of the other phenolic hydroxyl group-containing compound (E) used herein include phenol, dihydroxybenzene, phenylphenol, bisphenol, naphthol, and dihydroxynaphthalene. These may be used alone or in combination of two or more. In the case of using another phenolic hydroxyl group-containing compound (E), it is preferred that the total amount of the phenolic hydroxyl group-containing compound raw material of the novolac resin intermediate (M) is 100 mass from the viewpoint of sufficiently exerting the effects of the present invention. In the above, the triarylmethane type compound (A) and the phenol compound (B) are used in an amount of 50 parts by mass or more, and more preferably 80 parts by mass or more.

The above-mentioned triarylmethane type compound (A) and the above phenol compound (B) can be obtained by suppressing excessive polymerization (gelation) to obtain a phenolic hydroxyl group-containing resin having a molecular weight of a suitable composition for a resist. And the reaction molar ratio [[(A) + (B)) / (C)]) of the above aldehyde compound (C) is preferably in the range of 1/0.5 to 1/1.2, more preferably 1/0.6 to 1/1. The range of 0.9.

When the above-mentioned other phenolic hydroxyl group-containing compound (E) is used in combination, the molar ratio of the total of the phenolic hydroxyl group-containing compound raw materials (P) to the above aldehyde compound (C) [(P)/(C)] It is preferably in the range of 1/0.5 to 1/1.2, more preferably in the range of 1/0.6 to 1/0.9.

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

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

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

After completion of the reaction, water is added to the reaction product to carry out a reprecipitation operation or the like, whereby a novolak resin intermediate (M) can be obtained. The weight average molecular weight of the novolac resin intermediate (M) obtained in this manner for a resin having a phenolic hydroxyl group which is excellent in balance of developability, heat resistance and crack resistance. (Mw) is preferably in the range of 3,000 to 50,000. Further, the polydispersity (Mw/Mn) of the phenolic hydroxyl group-containing resin is preferably in the range of 3 to 10.

In the present invention, the weight average molecular weight (Mw) and the polydispersity (Mw/Mn) are values measured by GPC under the following conditions.

[Measurement conditions of GPC]

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

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

Column temperature: 40 ° C

Detector: RI (differential refractometer)

Data Processing: Tosoh Corporation produces "GPC-8020 Model II Version 4.30"

Developing solvent: tetrahydrofuran

Flow rate: 1.0 mL/min

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

Standard sample: monodisperse polystyrene described below

(Standard sample: monodisperse polystyrene)

Tosoh Co., Ltd. manufactures "A-500"

Tosoh Co., Ltd. manufactures "A-2500"

Tosoh Co., Ltd. manufactures "A-5000"

Tosoh Co., Ltd. manufactures "F-1"

Tosoh Co., Ltd. manufactures "F-2"

Tosoh Corporation produces "F-4"

Tosoh Co., Ltd. manufactures "F-10"

Tosoh Co., Ltd. manufactures "F-20"

The olefin 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), and examples thereof include the following A compound represented by the formula (6).

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

The olefin compound (D) having 8 to 24 carbon atoms may be used alone or in combination of two or more.

R ⁶ in the above structural formula (6) may be either a linear type or a branched structure as long as it is an aliphatic hydrocarbon group having 6 to 22 carbon atoms, or may have a structure Any one of a saturated base and no unsaturated base. Among them, in the case of a phenolic hydroxyl group-containing resin which is particularly excellent in crack resistance, R ^{6 is} preferably a linear alkyl group, and the carbon number thereof is particularly preferably in the range of 6 to 18.

The reaction ratio of the above-mentioned novolak resin intermediate (M) to the olefin compound (D) having 8 to 24 carbon atoms in the resin having a phenolic hydroxyl group which is excellent in balance between developability, heat resistance and crack resistance. The ratio of the total amount of the phenolic resin intermediate (M) to the olefin compound (D) having 8 to 24 carbon atoms is preferably 0.5 to 30% by mass based on the total weight of the olefin compound (D) having 8 to 24 carbon atoms. .

The reaction of the above-mentioned novolak resin intermediate (M) with the ethylenic compound (D) having 8 to 24 carbon atoms is preferably carried out under acid catalyst conditions. Examples of the acid catalyst used herein include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts may be used alone or in combination of two or more. Among these, sulfuric acid is preferred in terms of excellent catalyst activity.

The reaction of the above-mentioned novolak resin intermediate (M) with the ethylenic compound (D) having 8 to 24 carbon atoms can also be carried out in an organic solvent as needed. Examples of the solvent to be used herein include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol. 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin Polyol; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol a glycol ether such as ether, ethylene glycol ethyl methyl ether or ethylene glycol monophenyl ether; Alkane, 1,4-two a cyclic ether such as an alkane or a tetrahydrofuran; a glycol ester such as ethylene glycol acetate; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone. These solvents may be used singly or in combination of two or more kinds.

The reaction of the above-mentioned novolak resin intermediate (M) with the olefin compound (D) having 8 to 24 carbon atoms is carried out, for example, at a temperature ranging from 60 to 140 ° C for 0.5 to 20 hours.

After the completion of the reaction, water is added to the reaction product to carry out a reprecipitation operation, and the organic solvent or the like is appropriately washed to obtain a desired phenolic hydroxyl group-containing resin. The resin having a phenolic hydroxyl group obtained in this manner preferably has a weight average molecular weight (Mw) of 3,500~ which is excellent in balance between developability, heat resistance and crack resistance and is suitable for a resist material. A range of 50,000. Further, the polydispersity (Mw/Mn) of the phenolic hydroxyl group-containing resin is preferably in the range of 3 to 10.

The phenolic hydroxyl group-containing resin of the present invention described above is particularly useful as a resist material because of its excellent balance of developability, heat resistance and crack resistance, and is also dissolved in a general organic solvent. It is excellent in properties and the like, and is easy to handle. Therefore, it can be used in various applications such as coatings, adhesives, printed wiring boards, and the like for various electrical and electronic component applications. When the phenolic hydroxyl group-containing resin of the present invention is used for a resist material, the specific use thereof is not particularly limited, and it is preferably used for a thick film application or a resist base film or a resist. Permanent film use.

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

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

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

In addition to the above-mentioned 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). Examples of the other resin (X) used herein include, for example, various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, compounds containing phenolic hydroxyl groups, and alkoxy groups. Modified aromatic novolac resin, phenol aralkyl resin (ZYLOCK resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenol ethane resin, biphenyl modified phenol resin, Benzene modified naphthol resin, amine base three Modified phenolic resin, and various vinyl polymers.

More specifically, examples of the above-mentioned various novolak resins include phenols such as alkylphenols such as phenol, cresol or xylenol, phenylphenol, resorcin, biphenyl, bisphenol A or bisphenol F; A polymer obtained by reacting a phenolic hydroxyl group-containing compound such as naphthol or dihydroxynaphthalene with an aldehyde compound under an acid catalyst condition.

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

In the case of using these other resins, the blending ratio of the phenolic hydroxyl group-containing resin of the present invention to the other resin (X) can be arbitrarily set depending on the use, but the effect exerted by the present invention is more remarkably exhibited. In other words, it is preferable that the other resin (X) is in a ratio of 0.5 to 100 parts by mass based on 100 parts by mass of the phenolic hydroxyl group-containing resin of the present invention.

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

The photosensitive composition of the present invention may contain a surfactant for the purpose of improving the adhesion of the film forming property or the pattern in the case of using the resist. The surfactant used herein may, for example, be a polyoxyethylene alkyl ether compound such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether or polyoxyethylene oleyl ether, or the like. Polyoxyethylene alkyl allyl ether compound such as oxyethylene octyl phenol ether or polyoxyethylene nonyl phenol ether, polyoxyethylene-polyoxypropylene block copolymer, sorbitan monolaurate, sorbitan single palm A sorbitan fatty acid ester compound such as an acid ester, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, or polyoxyethylene sorbitol Anhydride monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate a nonionic surfactant such as a polyoxyethylene sorbitan fatty acid ester compound such as an ester; a copolymer of a fluoroaliphatic group-containing polymerizable monomer and [poly(oxyalkylene)](meth)acrylate; a fluorine-based surfactant having a fluorine atom in a molecular structure; having a polyfluorene in a molecular structure A polyoxo-based surfactant such as an oxygen structure site. These may be used alone or in combination of two or more.

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

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

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

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

The method of photolithography using the above-mentioned photosensitive resist material is applied, for example, to a substrate on which a ruthenium substrate is subjected to photolithography, and a resist material is applied, and pre-baked at a temperature of 60 to 150 °C. The coating method at this time may be any one of spin coating, roll coating, flow coating, dip coating, spray coating, blade coating, and the like. When the resist material of the present invention is used as a positive type, the target resist pattern is exposed through a specific mask, and the exposed portion is dissolved by an alkali developing solution, thereby forming a resist pattern. Since the resist material of the present invention has high alkali solubility in the exposed portion and alkali resistance in the non-exposed portion, a resist pattern having excellent resolution can be formed.

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

More specifically, examples of the above-mentioned various novolak resins include phenols such as alkylphenols such as phenol, cresol or xylenol, phenylphenol, resorcin, biphenyl, bisphenol A or bisphenol F; A polymer obtained by reacting a phenolic hydroxyl group-containing compound such as naphthol or dihydroxynaphthalene with an aldehyde compound under an acid catalyst condition.

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

In the case of using these other resins, the blend ratio of the phenolic hydroxyl group-containing resin of the present invention to the other resin (Y) can be arbitrarily set depending on the use, but the effect exerted by the present invention is more remarkably exhibited. In other words, the resin (Y) is preferably used in an amount of from 0.5 to 100 parts by mass based on 100 parts by mass of the phenolic hydroxyl group-containing resin of the present invention.

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

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

Examples of the melamine compound include a compound obtained by methoxymethylation of hexamethylenemethyl melamine, hexamethoxymethyl melamine, hexamethylol melamine, and hexamethoxyethyl melamine, and hexamethoxyethyl group. A compound obtained by methylating a methoxy group of 1 to 6 hydroxymethyl groups of melamine, hexamethoxymethyl melamine or hexamethylol melamine.

Examples of the above guanamine compound include 1,4-hydroxymethyl decylamine, tetramethoxymethyl decylamine, tetramethoxymethyl benzoguanamine, and tetrahydroxymethyl decylamine. A compound obtained by oxymethylation, tetramethoxyethylguanamine, tetradecyloxyguanamine, tetrahydroxymethylamine, 1 to 4 methylol groups, methylated by a methoxy group Compounds, etc.

The above-mentioned glycoluril compound may, for example, be 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycolil, 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-tetra(butoxymethyl)urea, and 1,1,3,3-tetra(methoxy). Methyl)urea and the like.

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

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

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

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

Examples of the compound containing a double bond such as an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propylene glycol divinyl ether, and 1,4-butanediol divinyl ether. Tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, neopentyl alcohol Trivinyl ether, neopentyl alcohol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, and the like.

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

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

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

When the curable composition of the present invention is used for a resist application, in addition to the phenolic hydroxyl group-containing resin and the curing agent of the present invention, other resin (Y), a surfactant or a dye may be added as needed. Various additives such as a filler, a crosslinking agent, and a dissolution promoter are dissolved in an organic solvent, whereby a curable resist material can be obtained.

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

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

When the resist base film is formed of the above-described resist material, the resist base film is formed by, for example, applying the resist material to a target for photolithography such as a ruthenium substrate. After drying at a temperature of ~200 ° C, it is further cured by heating at a temperature of 250 to 400 ° C. Then, a normal resist photolithography operation is performed on the base film to form a resist pattern, and a dry etching process is performed by a halogen-based plasma gas or the like, whereby a resist pattern can be formed by a multilayer resist method.

[Examples]

Hereinafter, the present invention will be described in more detail by way of specific examples. Further, the number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity (Mw/Mn) of the synthesized resin are measured under the measurement conditions of GPC described below.

[Measurement conditions of GPC]

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

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

Column temperature: 40 ° C

Detector: RI (differential refractometer)

Data Processing: Tosoh Corporation produces "GPC-8020 Model II Version 4.30"

Developing solvent: tetrahydrofuran

Flow rate: 1.0 mL/min

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

Injection volume: 0.1mL

Standard sample: monodisperse polystyrene described below

(Standard sample: monodisperse polystyrene)

Tosoh Co., Ltd. manufactures "A-500"

Tosoh Co., Ltd. manufactures "A-2500"

Tosoh Co., Ltd. manufactures "A-5000"

Tosoh Co., Ltd. manufactures "F-1"

Tosoh Co., Ltd. manufactures "F-2"

Tosoh Corporation produces "F-4"

Tosoh Co., Ltd. manufactures "F-10"

Tosoh Co., Ltd. manufactures "F-20"

Further, in the measurement of the ¹³ C-NMR spectrum, "AL-400" was produced by using Nippon Electronics Co., Ltd., and the DMSO-d ₆ solution of the sample was analyzed to carry out structural analysis. Hereinafter, the measurement conditions of the ¹³ C-NMR spectrum are shown.

[ ¹³ C-NMR Spectrometric Conditions]

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

Pulse angle: 45 ° C pulse

Sample concentration: 30wt%

Cumulative number: 10,000 times

Production Example 1 Production of Triarylmethane Compound (A-1)

To a 3,000-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. While adding 30 ml of sulfuric acid while cooling in an ice bath, the mixture was heated to 100 ° C by a mantle heater and allowed to react while stirring for 2 hours. After the reaction, water was added to the obtained solution to reprecipitate the crude product. The obtained crude product was redissolved in acetone, and further reprecipitated with water, and the precipitate was separated by filtration and dried in vacuo to obtain 421 g of a white crystalline triarylmethane type compound (A-1). The formation of the compound represented by the following structural formula was confirmed by ¹³ C-NMR. Further, the purity calculated from the GPC chart was 98.2% of GPC purity. The GPC line of the triarylmethane type compound (A-1) is shown in Fig. 1, and the ¹³ C-NMR line is shown in Fig. 2.

Production Example 2 Production of Novolak Resin Intermediate (M-1)

174 g of the above triarylmethane type compound (A-1) and 54 g of m-cresol were added to a 3,000-ml four-necked flask equipped with a cooling tube, and then dissolved in 500 ml of 2-ethoxyethanol and 500 ml of acetic acid. While adding 50 ml of sulfuric acid while cooling in an ice bath, 33 g of 92% paraformaldehyde was added. The mixture was heated to 80 ° C in an oil bath and allowed to react while stirring for 10 hours. After the end 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 separated by filtration and vacuum dried to obtain 213 g of a red powder novolak resin intermediate (M-1). The novolak resin intermediate (M-1) had a number average molecular weight (Mn) of 1,937, a weight average molecular weight (Mw) of 12,822, and a polydispersity (Mw/Mn) of 6.62.

Production Example 3 Production of Novolak Resin Intermediate (M-2)

249 g of the above triarylmethane type compound (A-1) and 31 g of m-cresol were added to a 3,000-ml four-necked flask equipped with a cooling tube, and then dissolved in 500 ml of 2-ethoxyethanol and 500 ml of acetic acid. While adding 50 ml of sulfuric acid while cooling in an ice bath, 33 g of 92% paraformaldehyde was added. The mixture was heated to 80 ° C in an oil bath and allowed to react while stirring for 10 hours. After the end of the reaction, water was added to the obtained solution to reprecipitate the crude product. The crude product was redissolved in acetone, and reprecipitated by water. The precipitate was separated by filtration and vacuum dried to obtain 266 g of a red powder novolak resin intermediate (M-2). The novolak resin intermediate (M-2) had a number average molecular weight (Mn) of 2,018, a weight average molecular weight (Mw) of 11,486, and a polydispersity (Mw/Mn) of 5.69.

Production Example 4 Production of Novolak Resin Intermediate (M-3)

174 g of the above triarylmethane type compound (A-1) and 54 g of m-cresol were added to a 3,000-ml four-necked flask equipped with a cooling tube, and then dissolved in 500 ml of 2-ethoxyethanol and 500 ml of acetic acid. After adding 50 ml of sulfuric acid while cooling in an ice bath, 30 g of 92% paraformaldehyde was added. The mixture was heated to 80 ° C in an oil bath and allowed to react while stirring for 8 hours. After the end 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 separated by filtration and vacuum dried to obtain 218 g of a red powder novolak resin intermediate (M-3). The novolak resin intermediate (M-3) had a number average molecular weight (Mn) of 1,538, a weight average molecular weight (Mw) of 6,508, and a polydispersity (Mw/Mn) of 4.23.

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

To a four-necked flask of 300 ml in which a cooling tube was placed, 30 g of a novolak resin intermediate (M-1) and 3.0 g of 1-octene were added, and then dissolved in 100 ml of 2-ethoxyethanol. After adding 10 ml of sulfuric acid while cooling in an ice bath, the mixture was heated to 80 ° C in an oil bath and allowed to react while stirring for 6 hours. After the end of the reaction, water was added to the obtained solution to reprecipitate the crude product. Next, the crude product was dissolved in methanol, and then hexane was added thereto to reprecipitate, and the precipitate was separated by filtration, and vacuum-dried to obtain 29 g of a red powdery phenolic hydroxyl group-containing resin (1). The phenolic hydroxyl group-containing resin (1) had a number average molecular weight (Mn) of 1,827, a weight average molecular weight (Mw) of 12,209, and a polydispersity (Mw/Mn) of 6.68. The GPC line of the phenolic hydroxyl group-containing resin (1) is shown in Fig. 3.

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

The same operation as in Example 1 was carried out except that 3.0 g of 1-octene was changed to 1.5 g of 1-octadecene, thereby obtaining 27 g of a red powder phenolic hydroxyl group-containing resin (2). The phenolic hydroxyl group-containing resin (2) had a number average molecular weight (Mn) of 1,860, a weight average molecular weight (Mw) of 13,740, and a polydispersity (Mw/Mn) of 7.39. The GPC line of the phenolic hydroxyl group-containing resin (2) is shown in Fig. 4 .

Example 3 Production of Resin Containing Phenolic Hydroxyl Group (3)

In addition to changing 30 g of the novolak resin intermediate (M-1) to 30 g of the novolak resin intermediate (M-2), and changing 1-100 of 1-octene to 3.0 g of 1-dodecene, the same procedure as in Example 1 was carried out. The same operation was carried out to obtain 30 g of a phenolic hydroxyl group-containing resin (3) of a red powder. The phenolic hydroxyl group-containing resin (3) had a number average molecular weight (Mn) of 2,010, a weight average molecular weight (Mw) of 10,756, and a polydispersity (Mw/Mn) of 5.35. The GPC line of the phenolic hydroxyl group-containing resin (3) is shown in Fig. 5.

Example 4 Production of Resin Containing Phenolic Hydroxyl Group (4)

In addition to changing 30 g of the novolak resin intermediate (M-1) to 30 g of the novolac resin intermediate (M-3), and changing 1-100 of 1-octene to 1.5 g of 1-dodecene, the same procedure as in Example 1 was carried out. The same operation was carried out to obtain 28 g of a red powder phenolic hydroxyl group-containing resin (4). The phenolic hydroxyl group-containing resin (4) had a number average molecular weight (Mn) of 1,572, a weight average molecular weight (Mw) of 6,784, and a polydispersity (Mw/Mn) of 4.32. The GPC line of the phenolic hydroxyl group-containing resin (4) is shown in Fig. 6.

Example 5 Production of Resin Containing Phenolic Hydroxyl Group (5)

In addition, 30 g of the novolak 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 "Linearen 148" manufactured by Idemitsu Kosan Co., Ltd. [1 The same operation as in Example 1 except that the mixture of tetradecene, 1-hexadecene and 1-octadecene 35:37:28 (mole ratio) was 1.5 g, thereby obtaining phenolic property of the red powder Hydroxyl resin (5) 29 g. The phenolic hydroxyl group-containing resin (5) had a number average molecular weight (Mn) of 1,586, a weight average molecular weight (Mw) of 6,829, and a polydispersity (Mw/Mn) of 4.31. The GPC line of the phenolic hydroxyl group-containing resin (5) is shown in Fig. 7.

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

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

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

To a four-necked flask of 300 ml in which a cooling tube was placed, 13.0 g of m-cresol, 8.6 g of p-cresol and 6.1 g of 3-pentadecylphenol were added, and then dissolved in 15 ml of 2-ethoxyethanol, acetic acid. 15ml. After adding 10 ml of sulfuric acid while cooling in an ice bath, 6.5 g of 92% paraformaldehyde was added. The mixture was heated to 80 ° C in an oil bath and allowed to react while stirring for 10 hours. After the end of the reaction, water was added to the obtained solution to reprecipitate the crude product. The crude product was redissolved in acetone, and reprecipitated by water. The precipitate was separated by filtration and dried in vacuo to obtain 24.6 g of a phenolic hydroxyl group-containing resin (2') as a yellow powder. The phenolic hydroxyl group-containing resin (2') had a number average molecular weight (Mn) of 1,792, a weight average molecular weight (Mw) of 11,701, and a polydispersity (Mw/Mn) of 6.53.

Examples 6 to 10 and Comparative Examples 1, 2

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

Preparation of photosensitive composition

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 12 parts by mass of a photosensitive agent was added to the solution and dissolved. This was filtered with a 0.2 μm membrane filter to obtain a photosensitive composition.

The sensitizer is manufactured by Toyo Synthetic Industrial Co., Ltd. and manufactured by "P-200" (4,4'-[1-[4-[1-(4-hydroxyphenyl)-1methylethyl]phenyl]) Base] bisphenol 1 molar and 1,2-naphthoquinone-2-diazide-5-chlorinated sulfonium 2 molar condensate).

Preparation of heat resistance test composition

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 the mixture was filtered through a 0.2 μm membrane filter to obtain a heat resistance test composition.

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

The photosensitive composition obtained above was applied onto a 5-inch wafer by a spin coater to a thickness of about 1 μm, and dried on a hot plate at 110 ° C for 60 seconds. Two wafers are prepared, and one is set to "unexposed sample". The other one was set as the "exposed sample", and the ghi ray of 100 mJ/cm ^{2 was} irradiated with a ghi ray lamp ("Multi-Light" manufactured by Ngau Electric Co., Ltd.), and then heat-treated at 140 ° C for 60 seconds. .

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

Evaluation of light sensitivity

The photosensitive composition obtained above was applied onto a 5-inch wafer by a spin coater to a thickness of about 1 μm, and dried on a hot plate at 110 ° C for 60 seconds. Ghi ray lamp (Niuwei Motor Co., Ltd.) is used after the mask corresponding to the resist pattern set in the range of 1 to 10 μm in line and gap is 1:1 and the line width is in the range of 1 to 10 μm. The "Multi-Light" was produced and irradiated with ghi rays, and heat treatment was performed at 140 ° C for 60 seconds. Then, after immersing in an alkali developing solution (2.38 % aqueous solution of tetramethylammonium hydroxide) for 60 seconds, it was dried on a hot plate at 110 ° C for 60 seconds.

Ghi ray exposure amount to make self 30mJ / cm ² to 10mJ / cm ² in order to increase the unit case can be faithfully reproduced 3μm width of the exposure amount (exposure amount Eop) was evaluated.

Evaluation of resolution

The photosensitive composition obtained above was applied onto a 5-inch wafer by a spin coater to a thickness of about 1 μm, and dried on a hot plate at 110 ° C for 60 seconds. A photomask was placed on the obtained wafer, and a ghi ray of 200 mJ/cm ^{2 was} irradiated by the same method as the above-described alkali developability evaluation to carry out an alkali development operation. When the state of the pattern was confirmed using a laser microscope ("VK-X200" manufactured by Keyence Co., Ltd.), it was evaluated as ○ with L/S = 5 μm, and × with L/S = 5 μm.

Heat resistance evaluation

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

Evaluation of crack resistance

The photosensitive composition obtained above was applied onto a 5 inch wafer by a spin coater, and dried on a hot plate at 110 ° C for 300 seconds. This coating operation was repeated to prepare a wafer having a coating film thickness of 50 μm and a wafer having a coating film thickness of 100 μm. The surface of the wafer was observed using a laser microscope ("VK-X200" manufactured by Keyence Co., Ltd.), and the case where no crack occurred was evaluated as ○, and the case where crack occurred was evaluated as ×.

Evaluation of softness

The photosensitive composition obtained above was applied onto a polyimine film having a thickness of 50 μm by 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 by 180 degrees, and the state of the bent portion was observed using a laser microscope ("VK-X200" manufactured by Keyence Co., Ltd.), and the crack-free condition was evaluated as ○, and cracking occurred. The situation was evaluated as ×.

Examples 11 to 15 and Comparative Examples 3 and 4

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

Preparation of hardenable composition

Dissolving 4 parts by mass of the phenolic hydroxyl group-containing resin and 4 parts by mass of a curing agent ("1,3,4,6-tetrakis(methoxymethyl) glycoluril" manufactured by Tokyo Chemical Industry Co., Ltd.) in propylene glycol 30 parts by mass of methyl ether acetate was filtered through a 0.2 μm membrane filter to obtain a curable composition.

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

The curable composition obtained above was applied onto a 5 inch wafer by a spin coater to a thickness of about 1 μm, and dried on a hot plate at 110 ° C for 60 seconds. Two wafers were prepared, and one was set to "unhardened sample". The other "hardened sample" was heat-treated at 160 ° C for 60 seconds.

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

Heat resistance evaluation

The curable composition obtained above was applied onto a 5 inch wafer by a spin coater at a thickness of about 1 μm, dried on a hot plate at 110 ° C for 60 seconds, and then at 160 ° C. Heat treatment was carried out for 60 seconds. The resin composition was scraped from the obtained wafer, and the glass transition temperature (Tg) thereof was measured. The glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC) ("Q100" manufactured by TA Instruments Co., Ltd.) under a nitrogen atmosphere at a temperature range of -100 to 250 ° C and a temperature rise temperature of 10 ° C / min. Under the conditions.

Crack resistance

The curable composition obtained above was applied onto a 5 inch wafer by a spin coater, and dried on a hot plate at 110 ° C for 300 seconds. This coating operation was repeated to prepare a wafer having a coating film thickness of 50 μm and a wafer having a coating film thickness of 100 μm. The surface of the wafer was observed using a laser microscope ("VK-X200" manufactured by Keyence Co., Ltd.), and the case where no crack occurred was evaluated as ○, and the case where crack occurred was evaluated as ×.

Claims (9)

A phenolic hydroxyl group-containing resin having a structural moiety (α) represented by the following structural formula (1) or (2) and a structural moiety (β) represented by the following structural formula (3) as a repeating unit; 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. (wherein 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, and ² ; and R ² and R ³ are each independently an aliphatic hydrocarbon group, and Any one of a hydrocarbon group, an alkoxy group and a halogen atom of an aromatic ring; l each independently an integer of 0 or 1 to 4; m is an integer of 0 or 1 to 5; n is an integer of 0 or 1 to 7; For the bond to the benzene ring or naphthalene ring shown in the figure, the two * may also be bonded to the same aromatic ring or may be bonded to a different aromatic ring) (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; and R ⁵ is a hydrogen atom or a carbon atom; 8 to 24 aliphatic hydrocarbon groups).  The phenolic hydroxyl group-containing resin according to claim 1, wherein the ratio ([α)/(β)] of the structural portion (α) to the structural portion (β) is 90/10 to 30/70. range.   A phenolic hydroxyl group-containing resin which is a reaction product of a novolak resin intermediate (M) and an olefin compound (D) having 8 to 24 carbon atoms; the novolac resin intermediate (M) has a lower a triarylmethane type compound (A) having a molecular structure represented by the formula (4) or (5), a phenol compound (B) having a phenol or an aliphatic hydrocarbon group having 1 to 7 carbon atoms, and an aldehyde compound (C) As a raw material for the reaction, (wherein k is 0, 1, or ² ; and R ² and R ³ are each independently an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, or a halogen atom; Is an integer of 0 or 1~4; m is an integer of 0 or 1~5; n is an integer of 0 or 1~7).  The phenolic hydroxyl group-containing resin according to claim 3, wherein the reaction ratio of the above-mentioned novolak resin intermediate (M) to the above-mentioned olefin compound (D) having 8 to 24 carbon atoms is the following ratio: The total mass of the above-mentioned olefin compound (D) having 8 to 24 carbon atoms is 0.5 to 30% by mass.    A photosensitive composition containing the phenolic hydroxyl group-containing resin according to any one of claims 1 to 4 and a sensitizer.    A resist material using the photosensitive composition of claim 5.    A curable composition containing the phenolic hydroxyl group-containing resin according to any one of claims 1 to 4 and a curing agent.    A cured product which is a cured product of the curable composition of claim 7.    A resist material using the curable composition of claim 7.