TWI763715B - Resin and resist material containing phenolic hydroxyl group - Google Patents

Abstract

The present invention provides a phenolic hydroxyl group-containing resin excellent not only in heat resistance and alkali developability but also in crack resistance when forming a thick film, a photosensitive composition containing the same, a curable composition, and a resist material . The present invention is a resin containing a phenolic hydroxyl group, characterized in that it has a structural moiety (α) represented by the following structural formula (1) or (2), and a structural moiety (α) represented by the following structural formula (3). β) 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.

(In the formula, 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)

(In the formula, R ⁴ is a hydrogen atom or an aliphatic hydrocarbon group with 1 to 7 carbon atoms. R ⁵ is a hydrogen atom or an aliphatic hydrocarbon group with 8 to 24 carbon atoms)

Description

Resin and resist material containing phenolic hydroxyl group

The present invention relates to a phenolic hydroxyl group-containing resin excellent not only in heat resistance and alkali developability but also in crack resistance when forming a thick film, a photosensitive composition containing the same, a curable composition, and a resist Material.

In the field of photoresist, various resist pattern formation methods subdivided according to the application and function have been successively developed, and along with this, the required performance of the resin material for resist has also been advanced and diversified. For example, in a resin material for pattern formation, high developability for forming a fine pattern with high production efficiency in a highly integrated semiconductor is required. In applications called base films, anti-reflection films, BARC films, hard masks, etc., not only dry etching resistance and low reflectivity are required, but also a thickness of tens of microns can be formed in the front-end field. film without cracking or cracking. Moreover, in the application called a resist permanent film etc., in addition to high heat resistance, it is also requested|required that a thick film can be formed, and it does not generate|occur|produce deterioration with time. Furthermore, from the viewpoint of quality reliability, long-term storage stability in various environments around the world is also one of the important properties.

The resins containing phenolic hydroxyl groups, which are the most widely used in photoresist applications, are cresol novolacs, but they are not capable of responding to the recent market demands of advanced and diversified development, and are also insufficient in heat resistance and developability. In addition, when a thick film is formed, cracks occur, so it is not suitable for use in thick film applications (refer to Patent Document 1).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Application 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 not only in heat resistance and alkali developability but also in crack resistance during thick film formation, a photosensitive composition containing the same, and a curability composition and resist material.

The inventors of the present invention have made diligent studies to solve the above-mentioned problems, and as a result, they have found that an alkene compound having 8 to 24 carbon atoms, a compound containing a phenolic hydroxyl group in the form of a triarylmethane, a phenol or aliphatic having 1 to 7 carbon atoms can be used. A phenolic hydroxyl group-containing resin obtained by reacting a phenolic compound of a family of hydrocarbon groups as a reaction raw material for a novolak resin intermediate is not only excellent in heat resistance and alkali developability, but also excellent in crack resistance when forming a thick film, thereby completing the present invention. invention.

That is, the present invention relates to a resin containing a phenolic hydroxyl group, which is characterized by having a structural moiety (α) represented by the following structural formula (1) or (2), and a structure represented by the following structural formula (3) The structural site (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.

(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, and 2. R ² and R ³ are independently aliphatic hydrocarbon groups, containing In any of the hydrocarbon group, alkoxy group and halogen atom of the aromatic ring, l is independently 0 or an integer of 1-4, m is an integer of 0 or 1-5, and n is an integer of 0 or 1-7.** It is a bonding point with the benzene ring or naphthalene ring shown in the figure, and the two * may be bonded with the same aromatic ring or with different aromatic rings)

(in the formula, R ¹ is any one of a hydrogen atom, an aliphatic hydrocarbon group, or a hydrocarbon group containing an aromatic ring. R ⁴ is a hydrogen atom or an aliphatic hydrocarbon group with 1 to 7 carbon atoms. R ⁵ is a hydrogen atom or a carbon atom number. 8~24 aliphatic hydrocarbon group)

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

(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, and l are each independently is 0 or an integer from 1 to 4, m is an integer from 0 or 1 to 5, and n is an integer from 0 or 1 to 7)

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

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

The present invention further relates to a curable composition comprising the above-mentioned 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-mentioned 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 not only in heat resistance and alkali developability, but also in crack resistance when forming a thick film, a photosensitive composition containing the same, a curable composition, and a resin containing a phenolic hydroxyl group. Etch material.

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

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

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

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

7 is a GPC diagram of the phenolic hydroxyl group-containing resin (5) obtained in Example 5. FIG.

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 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.

(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, and 2. R ² and R ³ are each independently an aliphatic hydrocarbon group, a hydrocarbon group containing In any of the hydrocarbon group, alkoxy group and halogen atom of the aromatic ring, l is independently 0 or an integer of 1-4, m is an integer of 0 or 1-5, and n is an integer of 0 or 1-7.** It is a bonding point with the benzene ring or naphthalene ring shown in the figure, and the two * may be bonded with the same aromatic ring or with different aromatic rings)

(in the formula, R ¹ is any one of a hydrogen atom, an aliphatic hydrocarbon group, or a hydrocarbon group containing an aromatic ring. R ⁴ is a hydrogen atom or an aliphatic hydrocarbon group with 1 to 7 carbon atoms. R ⁵ is a hydrogen atom or a carbon atom number. 8~24 aliphatic hydrocarbon group)

The phenolic hydroxyl group-containing resin of the present invention has the above-mentioned structural moiety (α) with high symmetry and rigidity as a repeating unit, and has a high density of phenolic hydroxyl groups, so it has the characteristics of high heat resistance and excellent developability. In the present invention, not only the above-mentioned structural part (α), but also the above-mentioned structural part (β) is used as a resin design as a repeating unit, and an aliphatic hydrocarbon group having 8 to 24 carbon atoms is introduced into the resin structure, thereby maintaining In the case of heat resistance and developability, it was successful in that the crack resistance also improved when forming a thick film. Generally speaking, the method of introducing a long-chain aliphatic hydrocarbon group into the resin structure to improve the flexibility or toughness of the resin has the effect of improving the crack resistance, but it is often accompanied by a decrease in the density of functional groups. The developability and heat resistance decrease, but in the present invention, there is no trade-off of such effects, and it becomes a phenolic hydroxyl group-containing resin excellent in any of developability, heat resistance, and crack resistance.

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

Regarding the above-mentioned structural site (α), * in the above-mentioned structural formulae (1) and (2) is a bonding point with any one of the three aromatic rings shown in the above-mentioned structural formulae (1) and (2) , 2 * can be bonded to the same aromatic ring, and can also be bonded to different aromatic rings respectively. Specifically, the structural part represented by the said structural formula (1) can be mentioned what is represented by any one of following structural formula (1-1)-(1-4). Moreover, the structural part represented by the said structural formula (2) is specifically, what is represented by any one of following structural formula (2-1)-(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, and 2. R ² and R ³ are independently aliphatic hydrocarbon groups, containing Any one of the hydrocarbon group, alkoxy group and halogen atom of the aromatic ring, l is independently 0 or an integer of 1 to 4, m is an integer of 0 or 1 to 5)

(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, and 2. R ² and R ³ are each independently an aliphatic hydrocarbon group, a hydrocarbon group containing Any one of the hydrocarbon group, alkoxy group and halogen atom of the aromatic ring, l is independently 0 or an integer of 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 a plurality of different structures. Among them, it is preferable to have a structural site represented by the above-mentioned structural formula (1) in order to be a phenolic hydroxyl group-containing resin excellent in the balance of developability, heat resistance, and crack resistance. Moreover, it is preferable that the value of k in the said structural formula (1), (2) is 1. When the value of k is 1, the bonding positions of the three phenolic hydroxyl groups in the structural formula (1) are preferably para positions with respect to the methine groups bonding the three aromatic rings.

R in the above-mentioned structural formulas (1) and ( ² ) is independently any one of aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, alkoxy group, and halogen atom, and l is independently 0 or one of 1 to 4. Integer. The above-mentioned aliphatic hydrocarbon group may be either of a straight-chain type or a branched structure, or may be any of those having an unsaturated group or not having an unsaturated group in the structure. The number of carbon atoms is not particularly limited, and may be any of a short chain having 1 to 6 carbon atoms and a relatively long chain having 7 or more carbon atoms. The specific structure of the above-mentioned 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, tolyl, xylyl, naphthyl, and anthracenyl, benzyl can also be exemplified: , Aralkyl such as phenylethyl, phenylpropyl, naphthylmethyl, etc. As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a cyclohexyloxy group etc. are mentioned, for example. As said halogen atom, a fluorine atom, a chlorine atom, and a bromine atom are mentioned.

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

R ³ in the above structural formulas (1) and (2) is independently any one of aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, alkoxy group, and halogen atom, m is 0 or an integer of 1 to 5, n It is 0 or an integer from 1 to 7. The above-mentioned aliphatic hydrocarbon group may be either of a straight-chain type or a branched structure, or may be any of those having an unsaturated group or not having an unsaturated group in the structure. The number of carbon atoms is not particularly limited, and may be any of a short chain having 1 to 6 carbon atoms and a relatively long chain having 7 or more carbon atoms. The specific structure of the above-mentioned 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, tolyl, xylyl, naphthyl, and anthracenyl, benzyl can also be exemplified: , Aralkyl such as phenylethyl, phenylpropyl, naphthylmethyl, etc. As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a cyclohexyloxy group etc. are mentioned, for example. As said halogen atom, a fluorine atom, a chlorine atom, and a bromine atom are mentioned. Among them, R ³ is preferably a hydrogen atom or an aliphatic hydrocarbon group having 9 to 24 carbon atoms in order to be a phenolic hydroxyl group-containing resin excellent in the balance of developability, heat resistance, and crack resistance.

Regarding the above-mentioned structural part (β), in the above-mentioned structural formula (3), 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 an aliphatic hydrocarbon group having 8 to 24 carbon atoms. These aliphatic hydrocarbon groups may be straight-chain or branched, or may have an unsaturated group in the structure, or may have no unsaturated group in the structure. Any of those having an unsaturated group and those not having an unsaturated group. . Among them, R ⁴ is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, more preferably a methyl group, in order to be a phenolic hydroxyl group-containing resin excellent in the balance of developability, heat resistance, and crack resistance. In addition, the substitution position is preferably a meta position with respect to the phenolic hydroxyl group.

In the phenolic hydroxyl group-containing resin of the present invention, the existence ratio of the above-mentioned structural moiety (α) and the above-mentioned structural moiety (β) is appropriately changed according to desired resin properties, applications, and the like. Among them, in order to obtain a phenolic hydroxyl group-containing resin excellent in the balance of developability, heat resistance, and crack resistance, the presence ratio [(α)/(β)] of both is preferably 90/10 to 30/ The range of 70 is preferably 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 of a straight-chain type or a branched chain structure, or may be any of those having an unsaturated group or a non-unsaturated group in the structure, or may be Any of those having an unsaturated group and those not having an unsaturated group in the structure. Among them, an aliphatic hydrocarbon group having 8 to 20 carbon atoms is preferable to be a phenolic hydroxyl group-containing resin having an excellent balance of developability, heat resistance, and crack resistance. Moreover, the alkyl group whose structure is a straight chain type is preferable.

For the phenolic hydroxyl group-containing resin excellent in the balance of developability, heat resistance, and crack resistance, the presence ratio of the aliphatic hydrocarbon group having 8 to 24 carbon atoms is preferably 100 parts by mass of the phenolic hydroxyl group-containing resin Among them, 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. For example, it can be produced by the following method. D) Reaction is carried out, and the novolak resin intermediate (M) is a triarylmethane type compound (A) having a molecular structure represented by the following structural formula (4) or (5), a phenol or a carbon number of 1 The phenolic compound (B) of the aliphatic hydrocarbon group of ~7, and the aldehyde compound (C) were used as reaction raw materials.

(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, and l are each independently is 0 or an integer from 1 to 4, m is an integer from 0 or 1 to 5, and n is an integer from 0 or 1 to 7)

The above-mentioned triarylmethane-type compound (A) may be used alone with the same structure, or a plurality of compounds having different molecular structures may be used in combination. Among them, as a phenolic hydroxyl group-containing resin excellent in the balance of developability, heat resistance, and crack resistance, one having the molecular structure represented by the above-mentioned structural formula (4) is preferred. Moreover, it is preferable that the value of k is 1. When 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 the para position with respect to the methine group bonding the three aromatic rings.

As said triarylmethane type compound (A), the thing obtained by the condensation reaction of a phenolic compound (a1) and an aromatic aldehyde compound (a2) is mentioned, for example. The above-mentioned phenol compound (a1) includes, for example, phenol or a compound in which one or more hydrogen atoms on the aromatic nucleus of phenol are substituted with an alkyl group, an alkoxy group, a halogen atom, or the like. These may be used independently, respectively, and may use 2 or more types together. Among them, it is preferable to have 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 the phenol in order to become a phenolic hydroxyl group-containing resin excellent in heat resistance The compound is preferably a compound having an alkyl group having 1 to 3 carbon atoms at the 2,5-position, particularly preferably 2,5-xylenol.

Examples of the above-mentioned aromatic aldehyde compound (a2) include compounds having a carboxyl group on an aromatic nucleus such as benzene, naphthalene, phenol, resorcinol, naphthol, and dihydroxynaphthalene, and a compound having an alkyl group in addition to the carboxyl group. , alkoxy, halogen atom and other compounds. These may be used independently, respectively, and may use 2 or more types together. Among them, in order to be a phenolic hydroxyl group-containing resin having an excellent balance between heat resistance and developability, those having a benzene ring structure are preferred, and specifically, benzaldehyde, sulfal, m-hydroxybenzaldehyde, Hydroxybenzaldehyde, more preferably sulfalal, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde.

In terms of obtaining the target triarylmethane type compound (A) in high yield and high purity, the reaction molar ratio [(a)/(b)] of the above-mentioned phenol compound (a1) and aromatic aldehyde compound (a2) is higher than The range of 1/0.2~1/0.5 is preferable, and the range of 1/0.25~1/0.45 is more preferable.

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

烷、1,4-二

烷、四氫呋喃等環狀醚；乙二醇乙酸酯等二醇酯；丙酮、甲基乙基酮、甲基異丁基酮等酮等。該等溶劑可分別單獨使用，亦可以2種以上之混合溶劑之形式使用。 The reaction of the phenolic compound (a1) and the aromatic aldehyde compound (a2) can also be carried out in an organic solvent as required. Examples of the solvent used here include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol. , 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin isopolyol; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoamyl ether, ethylene glycol dimethyl ether ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether and other glycol ethers; 1,3-di

Alkane, 1,4-di

Cyclic ethers such as alkane and tetrahydrofuran; glycol esters such as ethylene glycol acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. These solvents may be used alone or in the form of a mixed solvent of two or more.

The reaction of the above-mentioned phenol compound (a1) and the aromatic aldehyde compound (a2) is carried out, for example, in a temperature range of 60 to 140° C. for 0.5 to 20 hours.

After the reaction is completed, for example, by throwing the reaction product into a poor solvent (S1) of the triarylmethane type compound (A) and separating the precipitate by filtration, the solubility of the triarylmethane type compound (A) is then made high and is compatible with the triarylmethane type compound (A). The method for redissolving the precipitate obtained in the solvent (S2) mixed with the above-mentioned poor solvent (S1), removes the unreacted phenolic compound (a1) or aromatic aldehyde compound (a2), the acid contact compound used from the reaction product medium, so that purified triarylmethane-type compound (A) can be obtained.

When the reaction of the phenolic 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 obtain the triarylmethane type compound (A) By dissolving in an aromatic hydrocarbon solvent and cooling as it is, crystals of the above-mentioned triarylmethane type compound (A) can be precipitated.

Examples of the poor solvent (S1) used for the purification of the triarylmethane-type compound (A) include water; monoalcohols such as methanol, ethanol, propanol, and ethoxyethanol; n-hexane, n-heptane, n-octane, etc. Aliphatic hydrocarbons such as alkane and cyclohexane; aromatic hydrocarbons such as toluene and xylene. These may be used independently, respectively, and may use 2 or more types together. Among them, water, methanol, and ethoxyethanol are preferable because the solubility of the acid catalyst is excellent.

On the other hand, the above-mentioned solvent (S2) includes, for example, monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5 -Pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene Polyols such as glycol and glycerol; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoamyl ether, ethylene glycol Glycol ethers such as glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether; cyclic ethers such as 1,3-dioxane, 1,4-dioxane; ethylene glycol acetate, etc. Diol esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. These may be used independently, respectively, and may use 2 or more types together. Among these, when using water or a monoalcohol as the said poor solvent (S1), it is preferable to use acetone as a solvent (S2).

Regarding the above-mentioned phenol compound (B) having a phenol or 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, or Any of those having an unsaturated group in the structure and those not having an unsaturated group may be sufficient, and those having an unsaturated group in the structure and those not having an unsaturated group may be used. Among them, the phenolic compound (B) is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, preferably a phenolic hydroxyl group-containing resin having an excellent balance of developability, heat resistance, and crack resistance. Has methyl. In addition, the substitution position thereof is preferably the meta position with respect to the phenolic hydroxyl group.

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

The aldehyde compound (C) may be a novolac-type phenolic hydroxyl group-containing resin by condensation reaction with the triarylmethane-type compound (A) and the phenolic compound (B), and examples thereof include formaldehyde. , polyoxymethylene, 1,3,5-trioxane, acetaldehyde, propionaldehyde, tetramethylene, polyoxymethylene, trichloroacetaldehyde, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, hexanal, Allylaldehyde, crotonaldehyde, acrolein, etc. These may be used independently, respectively, and may use 2 or more types together. Among them, formaldehyde is preferably used in terms of excellent reactivity. Formaldehyde can be used in the form of formalin in the form of an aqueous solution, and can also be used in the form of paraformaldehyde in a solid state, either. Moreover, when formaldehyde and another aldehyde compound are used together, it is preferable to use another aldehyde compound in the ratio of 0.05-1 mol with respect to 1 mol of formaldehyde.

In addition to the above-mentioned triarylmethane type compound (A), the above-mentioned phenolic compound (B) and the above-mentioned aldehyde compound (C), the above-mentioned novolak resin intermediate (M) can also use other phenolic hydroxyl group-containing compounds (E) as a reaction raw material. As the other phenolic hydroxyl group-containing compound (E) used here, for example, phenol, dihydroxybenzene, phenylphenol, bisphenol, naphthol, and dihydroxynaphthalene can be mentioned. These may be used independently, respectively, and may use 2 or more types together. In the case of using other phenolic hydroxyl group-containing compound (E), the total amount of the phenolic hydroxyl group-containing compound raw material of the novolak resin intermediate (M) is preferably 100 mass in total in order to fully exhibit the effect of the present invention. Among the parts, 50 parts by mass or more of the above-mentioned triarylmethane type compound (A) and phenol compound (B) are used in total, more preferably 80 parts by mass or more.

The above triarylmethane type compound (A), the above phenolic compound (B ) and the reaction molar ratio of the above-mentioned aldehyde compound (C) [[(A)+(B)]/(C)] is preferably in the range of 1/0.5~1/1.2, more preferably 1/0.6~1/ 0.9 range.

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

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

烷、1,4-二

烷、四氫呋喃等環狀醚；乙二醇乙酸酯等二醇酯；丙酮、甲基乙基酮、甲基異丁基酮等酮等。該等溶劑可分別單獨使用，亦可以2種以上之混合溶劑之形式使用。 The reaction of the above-mentioned triarylmethane type compound (A), the above-mentioned phenol compound (B) and the above-mentioned aldehyde compound (C) can also be carried out in an organic solvent as required. Examples of the solvent used here include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol. , 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin isopolyol; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoamyl ether, ethylene glycol dimethyl ether ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether and other glycol ethers; 1,3-di

Alkane, 1,4-di

Cyclic ethers such as alkane and tetrahydrofuran; glycol esters such as ethylene glycol acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. These solvents may be used alone or in the form of a mixed solvent of two or more.

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

After completion of the reaction, water is added to the reaction product, and a reprecipitation operation or the like is performed to obtain a novolak resin intermediate (M). The weight average molecular weight of the novolak resin intermediate (M) obtained in this way in terms of obtaining a phenolic hydroxyl group-containing resin that is excellent in the balance of developability, heat resistance and crack resistance and is suitable for resist materials (Mw), Preferably it is the range of 3,000-50,000. In addition, the polydispersity (Mw/Mn) of the phenolic hydroxyl group-containing resin is preferably in the range of 3 to 10.

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

[Measurement conditions of GPC]

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

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" (8.0mmΦ) manufactured by Showa Denko Co., Ltd. ×300mm) + "Shodex KF804" made by Showa Denko Co., Ltd. (8.0mmΦ×300mm)

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 tetrahydrofuran solution of 0.5 mass % in terms of resin solid content was filtered with a microfilter (100 μl)

Standard sample: the following monodisperse polystyrene

(Standard sample: monodisperse polystyrene)

"A-500" manufactured by Tosoh Corporation

"A-2500" manufactured by Tosoh Corporation

"A-5000" manufactured by Tosoh Corporation

"F-1" manufactured by Tosoh Corporation

Tosoh Corporation's "F-2"

Tosoh Corporation's "F-4"

"F-10" manufactured by Tosoh Corporation

"F-20" manufactured by Tosoh Corporation

The alkene compound (D) having 8 to 24 carbon atoms is not particularly limited as long as it has an ethylenic double bond site that can react with the above-mentioned novolak resin intermediate (M), and the molecular structure other than that is not particularly limited, for example, the following The compound represented by the structural formula (6).

(in the formula, R ⁶ is an aliphatic hydrocarbon group with 6 to 22 carbon atoms)

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

In the above structural formula (6), as long as R ⁶ is an aliphatic hydrocarbon group having 6 to 22 carbon atoms, it can be either of a straight-chain type or a branched-chain structure, and it can also be a structure having a different structure. Any of those having a saturated group and those not having an unsaturated group. Among them, in order to be a phenolic hydroxyl group-containing resin with particularly excellent crack resistance, R ⁶ is preferably a straight-chain alkyl group, and the number of carbon atoms thereof is particularly preferably in the range of 6 to 18.

The reaction ratio between the above-mentioned novolak resin intermediate (M) and the olefinic compound (D) having 8 to 24 carbon atoms in order to become a phenolic hydroxyl group-containing resin excellent in the balance of developability, heat resistance, and crack resistance Preferably, the ratio of the olefinic compound (D) having 8 to 24 carbon atoms is 0.5 to 30% by mass relative to the total mass of the novolak resin intermediate (M) and the olefinic compound (D) having 8 to 24 carbon atoms. .

The reaction between the above-mentioned novolak resin intermediate (M) and the alkene compound (D) having 8 to 24 carbon atoms is preferably carried out under the condition of an acid catalyst. Examples of the acid catalyst used here include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, manganese acetate, and the like. These acid catalysts may be used alone or in combination of two or more. Among these, sulfuric acid is preferable in that it is excellent in catalyst activity.

烷、1,4-二

烷、四氫呋喃等環狀醚；乙二醇乙酸酯等二醇酯；丙酮、甲基乙基酮、甲基異丁基酮等酮等。該等溶劑可分別單獨使用，亦可以2種以上之混合溶劑之形式使用。 The reaction between the above-mentioned novolak resin intermediate (M) and the alkene compound (D) having 8 to 24 carbon atoms can also be carried out in an organic solvent as required. Examples of the solvent used here include: monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol , 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin isopolyol; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoamyl ether, ethylene glycol dimethyl ether ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether and other glycol ethers; 1,3-di

Alkane, 1,4-di

Cyclic ethers such as alkane and tetrahydrofuran; glycol esters such as ethylene glycol acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. These solvents may be used alone or in the form of a mixed solvent of two or more.

The reaction between the above-mentioned novolak resin intermediate (M) and the alkene compound (D) having 8 to 24 carbon atoms is performed, for example, in a temperature range of 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 reprecipitation operation, and appropriate use of an organic solvent or the like for washing, etc., can obtain the target phenolic hydroxyl group-containing resin. The weight average molecular weight (Mw) of the phenolic hydroxyl group-containing resin obtained in this way is preferably 3,500~ 50,000 range. In addition, 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 in detail above has the advantage of being excellent in the balance of developability, heat resistance and crack resistance, so it is particularly useful as a resist material, and is soluble in general-purpose organic solvents. Because of its excellent properties and easy handling, it can be used in various applications such as paints, adhesives, and various electrical and electronic component applications such as printed wiring boards. When the phenolic hydroxyl group-containing resin of the present invention is used as a resist material, its specific use is not particularly limited, and it can also be preferably used for thick film applications, resist base films, resist Permanent film use.

The photosensitive composition of the present invention contains the above-described phenolic hydroxyl group-containing resin and photosensitizer of the present invention as essential components. Specific examples of the compound having a quinonediazide group include aromatic (poly)hydroxy compounds and compounds having a quinonediazide group such as 1,2-naphthoquinone-2-diazide-5-sulfonic acid and the like. Complete ester compound, partial ester compound, amide or partial amide, etc. with sulfonic acid or its halide.

Examples of the above-mentioned aromatic (poly)hydroxy 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 ',4,4',5'-hexahydroxybenzophenone and other polyhydroxybenzophenone compounds; 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) base) propane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 4,4'-{1-[4-[ 1-(4-Hydroxyphenyl)-1-methylethyl]phenyl]ethylene}bisphenol, 3,3'-dimethyl-{1-[4-[2-(3-methyl) -4-hydroxyphenyl)-2-propyl]phenyl]ethylene}bisphenol and other bis[(poly)hydroxyphenyl]alkane compounds; tris(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl) -3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3 ,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5 -Dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane and other tris(hydroxyphenyl) ) methane compound or its methyl substituent; bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenyl Methane, bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane (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-hydroxyphenylmethane, 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-2-hydroxy-4-methylphenyl)- Bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methane compounds such as 4-hydroxyphenylmethane, or methyl substituted compounds thereof, and the like. These photosensitizers may be used alone, respectively, or two or more of them may be used in combination.

In order to obtain a photosensitive composition having excellent photosensitivity, the blending amount of the above-mentioned photosensitive agent in the photosensitive composition of the present invention is preferably 100 parts by mass relative to the total resin solid content of the photosensitive composition. The ratio of 5 to 50 parts by mass.

改質酚樹脂、及各種乙烯基聚合物等。 The photosensitive composition of this invention may use other resin (X) together other than the said phenolic hydroxyl group containing resin of this invention. Examples of other resins (X) used here include various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenolic compounds, phenolic hydroxyl group-containing compounds, and alkoxy group-containing compounds. Aromatic compounds modified novolac resin, phenol aralkyl resin (ZYLOCK resin), naphthol aralkyl resin, trimethylolmethane resin, tetraphenol ethane resin, biphenyl modified phenol resin, biphenyl Benzene modified naphthol resin, amino three

Modified phenol resin, and various vinyl polymers, etc.

More specifically, the above-mentioned various novolak resins include alkylphenols such as phenol, cresol, and xylenol, bisphenols such as phenylphenol, resorcinol, biphenyl, bisphenol A, or bisphenol F, Compounds containing phenolic hydroxyl groups, such as naphthol and dihydroxynaphthalene, are polymers obtained by reacting with aldehyde compounds under acid catalyst conditions.

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

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

In addition, in the case where the phenolic hydroxyl group-containing resin of the present invention is used as a sensitivity enhancer by taking advantage of the characteristics of excellent photosensitivity of the phenolic hydroxyl group-containing resin of the present invention, it is preferable that the amount of the resin containing The resin of a phenolic hydroxyl group is the range of 3-80 mass parts.

The photosensitive composition of the present invention may also contain a surfactant for the purpose of improving film-forming properties or pattern adhesion when used for a resist. Examples of the surfactant used here include polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkyl ether compounds, and the like. Oxyethylene octylphenol ether, polyoxyethylene nonylphenol ether and other polyoxyethylene alkyl allyl ether compounds, polyoxyethylene-polyoxypropylene block copolymer, sorbitan monolaurate, sorbitan monopalm Acid esters, sorbitan fatty acid ester compounds such as sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitol Anhydride monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearic acid Nonionic surfactants such as polyoxyethylene sorbitan fatty acid ester compounds such as esters; copolymers of polymerizable monomers with fluoroaliphatic groups and [poly(oxyalkylene)](meth)acrylates, etc. Fluorine-based surfactants with fluorine atoms in the molecular structure; polysiloxane-based surfactants with polysiloxane structure sites in the molecular structure, etc. These may be used independently, respectively, and may use 2 or more types together.

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

When the photosensitive composition of the present invention is used for resist applications, in addition to the phenolic hydroxyl group-containing resin and photosensitizer of the present invention, other resins (X) or surfactants, dyes, Various additives such as fillers, cross-linking agents, and dissolution accelerators can be dissolved in organic solvents to form photosensitive resist materials. This resist material may be used as a coating material as it is, or what is coated on a support film and desolvated may be used as a resist film. Examples of the support film when used as a resist film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate, which may be either a single-layer film or a multi-layer laminate film. In addition, the surface of the support film may be corona-treated or coated with a release agent.

烷等環式醚；2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、氧乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、甲酸乙酯、乙酸乙酯、乙酸丁酯、乙醯乙酸甲酯、乙醯乙酸乙酯等酯化合物，該等可分別單獨使用，亦可併用兩種以上。 The type of the above-mentioned organic solvent is not particularly limited, and examples thereof include alkylene glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and the like. Monoalkyl ethers; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol Monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and other alkylene glycol alkyl ether acetates; acetone, methyl ethyl ketone, cyclohexanone, methyl Ketone compounds such as amyl ketone; two

Cyclic ethers such as alkane; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2-hydroxy -Methyl 3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, ethyl acetate Ester compounds such as methyl acetonate and 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 mixer or the like. In addition, when the resist material contains a filler or a pigment, it can be prepared by dispersing or mixing using a dispersing device such as a dispersing mixer, a homogenizer, and a three-roll mill.

The photolithography method using the above-mentioned photosensitive resist material is, for example, coating a resist material on a silicon substrate, that is, the object to be subjected to photolithography, and pre-baking at a temperature of 60-150°C. The coating method at this time may be any method such as spin coating, roll coating, flow coating, dip coating, spray coating, and blade coating. When the resist material of the present invention is used as a positive type, the resist pattern of the target is exposed through a specific mask, and the exposed portion is dissolved with an alkali developer, thereby forming a resist pattern. The resist material of the present invention can form a resist pattern with excellent resolution because both the alkali solubility of the exposed part and the alkali solubility resistance of the non-exposed part are high.

改質酚樹脂、及各種乙烯基聚合物等。 The curable composition of the present invention contains the above-described phenolic hydroxyl group-containing resin of the present invention and a curing agent as essential components. Moreover, other resin (Y) other than the phenolic hydroxyl group containing resin of this invention mentioned above may be used together. Examples of other resins (Y) used here include various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenolic compounds, phenolic hydroxyl-containing compounds and alkoxy-containing compounds. Aromatic compounds modified novolac resin, phenol aralkyl resin (ZYLOCK resin), naphthol aralkyl resin, trimethylolmethane resin, tetraphenol ethane resin, biphenyl modified phenol resin, biphenyl Benzene modified naphthol resin, amino three

Modified phenol resin, and various vinyl polymers, etc.

More specifically, the above-mentioned various novolak resins include alkylphenols such as phenol, cresol, and xylenol, bisphenols such as phenylphenol, resorcinol, biphenyl, bisphenol A, or bisphenol F, Compounds containing phenolic hydroxyl groups, such as naphthol and dihydroxynaphthalene, are polymers obtained by reacting with aldehyde compounds under acid catalyst conditions.

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

In the case of using these other resins, the blending ratio of the phenolic hydroxyl group-containing resin and the other resin (Y) of the present invention can be arbitrarily set according to the application, but the effect of the present invention is more prominently exhibited. In other words, it is preferable that the other resin (Y) is in a ratio of 0.5 to 100 parts by mass relative to 100 parts by mass of the phenolic hydroxyl group-containing resin of the present invention.

The curing agent used in the present invention is not particularly limited as long as it is a compound capable of causing a curing reaction with the phenolic hydroxyl group-containing resin of the present invention, and various compounds can be used. Moreover, the hardening 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 a suitable method, such as thermal hardening and photohardening. Curing conditions such as heating temperature and time during thermal curing, type of light during photocuring, and exposure time are appropriately adjusted according to the type of curing agent or the type of curing accelerator described later.

唑啉化合物等。 Specific examples of the above-mentioned curing agent include melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, novolak resins, epoxy compounds, isocyanate compounds, azide compounds, and bismuth compounds including alkenyl ether groups. Bond compounds, acid anhydrides,

oxazoline compounds, etc.

The above-mentioned melamine compound includes, for example, hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, and hexamethoxyethyl Melamine, hexaoxymethyl melamine, 1~6 methylol groups of hexamethylol melamine are compounded by oxymethylation, etc.

The above-mentioned guanamine compounds include, for example, 1 to 4 methylol groups of tetramethylolguanamine, tetramethoxymethylguanamine, tetramethoxymethylbenzoguanamine, and tetramethylolguanamine. Oxymethylated compounds, tetramethoxyethylguanamine, tetraoxoguanamine, tetramethylolguanamine, 1~4 hydroxymethyl groups of oxomethylation compounds, etc.

As said glycoluril compound, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 4,6-tetrakis (hydroxymethyl) glycoluril, etc.

Examples of the urea compound include 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea methyl) urea, etc.

The above-mentioned resol resins include, for example, bisphenols such as phenol, cresol, and xylenol, alkylphenols such as phenylphenol, resorcinol, biphenyl, bisphenol A, and Hydroxynaphthalene is a polymer obtained by reacting phenolic hydroxyl group-containing compounds with aldehyde compounds under alkaline catalyst conditions.

Examples of the above-mentioned epoxy compound include diglycidyloxynaphthalene, phenol novolak epoxy resin, cresol novolak epoxy resin, naphthol novolak epoxy resin, and naphthol-phenol co- novolak epoxy resin. Epoxy resin, naphthol-cresol co-acetal type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, 1,1-bis(2,7-diglycidyl) Oxy-1-naphthyl) alkane, naphthyl ether type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, epoxy resin containing phosphorus atom, containing Polyglycidyl ethers of co-condensates of phenolic hydroxyl compounds and alkoxy-containing aromatic compounds, etc.

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

As said azide compound, 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylenebisazide, 4,4'-oxybisazide, etc. are mentioned, for example.

Examples of compounds containing double bonds such as alkenyl ether groups include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, Tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, neopentylerythritol Trivinyl ether, neotaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, etc.

Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and biphenyl tetracarboxylic acid dianhydride. Anhydride, 4,4'-(isopropylidene)diphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and other aromatic anhydrides; tetrahydrophthalic anhydride Acid anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride dodecenylsuccinic anhydride, trioxane Alicyclic carboxylic acid anhydrides such as tetrahydrophthalic anhydride, etc.

Among these, a glycoluril compound, a urea compound, and a novolak resin are preferable, and a glycoluril compound is particularly preferable in terms of being a curable composition excellent in curability or heat resistance of a cured product.

In order to obtain a composition excellent in curability, the compounding amount of the above-mentioned curing agent in the curable composition of the present invention is preferably 100 with respect to the total of the phenolic hydroxyl group-containing resin of the present invention and other resins (X) parts by mass, the ratio is 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 resins (Y), surfactants, dyes, Various additives such as fillers, cross-linking agents, and dissolution accelerators can be dissolved in an organic solvent to form a curable resist material.

烷等環式醚；2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、氧乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、甲酸乙酯、乙酸乙酯、乙酸丁酯、乙醯乙酸甲酯、乙醯乙酸乙酯等酯化合物，該等可分別單獨使用，亦可併用兩種以上。 The type of the above-mentioned organic solvent is not particularly limited, and examples thereof include alkylene glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and the like. Monoalkyl ethers; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol Monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and other alkylene glycol alkyl ether acetates; acetone, methyl ethyl ketone, cyclohexanone, methyl Ketone compounds such as amyl ketone; two

Cyclic ethers such as alkane; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2-hydroxy -Methyl 3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, ethyl acetate Ester compounds such as methyl acetonate and ethyl acetate may be used alone or in combination of two or more.

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

When the resist base film is produced from the above-mentioned resist material, the resist base film is formed by, for example, the following method: coating the above-mentioned resist material on an object to be subjected to photolithography, such as a silicon substrate, at 100° C. After drying at a temperature of ~200°C, it is further heated and hardened at a temperature of 250~400°C. Then, a resist pattern is formed by performing a normal photolithography operation on the base film, and a dry etching process is performed using a halogen-based plasma gas or the like, whereby a resist pattern can be formed by a multilayer resist method.

[Example]

Hereinafter, the present invention will be described in more detail with reference to specific examples. Furthermore, the number-average molecular weight (Mn), weight-average molecular weight (Mw), and polydispersity (Mw/Mn) of the synthesized resin were measured under the following GPC measurement conditions.

[Measurement conditions of GPC]

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

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" (8.0mmΦ) manufactured by Showa Denko Co., Ltd. ×300mm) + "Shodex KF804" made by Showa Denko Co., Ltd. (8.0mmΦ×300mm)

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: One obtained by filtering a tetrahydrofuran solution of 0.5 mass % in terms of resin solid content with a microfilter

Injection volume: 0.1mL

Standard sample: the following monodisperse polystyrene

(Standard sample: monodisperse polystyrene)

"A-500" manufactured by Tosoh Corporation

"A-2500" manufactured by Tosoh Corporation

"A-5000" manufactured by Tosoh Corporation

"F-1" manufactured by Tosoh Corporation

Tosoh Corporation's "F-2"

Tosoh Corporation's "F-4"

"F-10" manufactured by Tosoh Corporation

"F-20" manufactured by Tosoh Corporation

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

[ ¹³ C-NMR spectrum measurement conditions]

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

Pulse angle: 45℃ pulse

Sample concentration: 30wt%

Cumulative times: 10000 times

Production Example 1 Production of triarylmethane type compound (A-1)

586.4 g of 2,5-xylenol and 244 g of 4-hydroxybenzaldehyde were added to a 3000 ml four-necked flask provided with a cooling tube, and dissolved in 1000 ml of 2-ethoxyethanol. After adding 30 ml of sulfuric acid while cooling in an ice bath, it was heated to 100° C. with a mantle heater and reacted 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. The precipitate was separated by filtration and vacuum-dried to obtain 421 g of white crystal triarylmethane type compound (A-1). The formation of the compound represented by the following structural formula was confirmed by ¹³ C-NMR. In addition, the purity calculated from the GPC diagram was GPC purity of 98.2%. 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. 2 .

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

174 g of the above-mentioned triarylmethane type compound (A-1) and 54 g of m-cresol were added to a 3000 ml four-necked flask provided 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, 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 the reaction was completed, 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 residue was separated by filtration and vacuum-dried to obtain 213 g of a novolak resin intermediate (M-1) as a red powder. 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.

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

249 g of the above-mentioned triarylmethane type compound (A-1) and 31 g of m-cresol were added to a 3000 ml four-necked flask provided 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, 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 the reaction was completed, 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 residue was separated by filtration and vacuum-dried to obtain 266 g of a novolak resin intermediate (M-2) as a red powder. 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.

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

174 g of the above-mentioned triarylmethane type compound (A-1) and 54 g of m-cresol were added to a 3000 ml four-necked flask provided 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. It was heated to 80 degreeC in an oil bath, and it was made to react, stirring for 8 hours. After the reaction was completed, 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 residue was separated by filtration and vacuum-dried to obtain 218 g of a red powder 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 Production of phenolic hydroxyl group-containing resin (1)

To a 300 ml four-necked flask provided with a cooling pipe, 30 g of the 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 reacted with stirring for 6 hours. After the reaction was completed, water was added to the obtained solution to reprecipitate the crude product. Next, after dissolving the crude product in methanol, hexane was added to make it reprecipitate, the residue was separated by filtration, and vacuum-dried to obtain 29 g of a phenolic hydroxyl group-containing resin (1) as a red powder. The number average molecular weight (Mn) of the 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 diagram of the phenolic hydroxyl group-containing resin (1) is shown in FIG. 3 .

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

Except having changed 3.0 g of 1-octene to 1.5 g of 1-octadecene, the same operation as Example 1 was performed, and the phenolic hydroxyl group containing resin (2) 27g of a red powder was obtained. The number average molecular weight (Mn) of the 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 diagram of the phenolic hydroxyl group-containing resin (2) is shown in FIG. 4 .

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

The same procedure as Example 1 was carried out, except that 30 g of the novolak 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. By the same operation, 30 g of the phenolic hydroxyl group-containing resin (3) as a red powder was obtained. The number average molecular weight (Mn) of the phenolic hydroxyl group-containing resin (3) was 2,010, the weight average molecular weight (Mw) was 10,756, and the polydispersity (Mw/Mn) was 5.35. The GPC diagram of the phenolic hydroxyl group-containing resin (3) is shown in FIG. 5 .

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

The same procedure as in Example 1 was carried out, except that 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 1.5 g of 1-dodecene. By the same operation, 28 g of the phenolic hydroxyl group-containing resin (4) as a red powder was obtained. The number average molecular weight (Mn) of the 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 diagram of the phenolic hydroxyl group-containing resin (4) is shown in FIG. 6 .

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

In addition to changing 30 g of the novolak resin intermediate (M-1) to 30 g of the novolak resin intermediate (M-3), and changing 3.0 g of 1-octene to "Linearen 148" manufactured by Idemitsu Kosan Co., Ltd. [1 -The same operation as in Example 1 was carried out except that a 35:37:28 (molar ratio) mixture of tetradecene, 1-hexadecene, and 1-octadecene] 1.5 g, to obtain a red powder containing phenolic properties Resin of hydroxyl group (5) 29g. The number average molecular weight (Mn) of the 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 diagram of the phenolic hydroxyl group-containing resin (5) is shown in FIG. 7 .

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

To a 2-L four-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 added, and the reaction was performed by heating to 100°C. It was heated to 200°C under normal pressure to perform dehydration and distillation, and further vacuum distillation was performed at 230°C for 6 hours to obtain 736 g of a pale yellow solid resin (1') containing a phenolic hydroxyl group. The number average molecular weight (Mn) of the phenolic hydroxyl group-containing resin (1') was 1,450, the weight average molecular weight (Mw) was 10,316, and the polydispersity (Mw/Mn) was 7.12.

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

13.0 g of m-cresol, 8.6 g of p-cresol, and 6.1 g of 3-pentadecylphenol were added to a 300-ml four-necked flask equipped with a cooling tube, and dissolved in 15 ml of 2-ethoxyethanol and acetic acid. 15ml. After adding 10 ml of sulfuric acid 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 the reaction was completed, 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 filtrate was separated by filtration and vacuum-dried to obtain 24.6 g of a phenolic hydroxyl group-containing resin (2') as a yellow powder. 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 according to the following points. The results are shown in Table 1.

Preparation of photosensitive compositions

28 parts by mass of the above-mentioned 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 sensitizer was added to the solution and dissolved. This was filtered with a 0.2 μm thin film filter to obtain a photosensitive composition.

"P-200" (4,4'-[1-[4-[1-(4-hydroxyphenyl)-1methylethyl]phenyl]ethylene (4,4'-[1-[4-[1-(4-hydroxyphenyl)-1methylethyl]phenyl]ethylene) base] 1 mol of bisphenol and 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride condensate).

Preparation of composition for heat resistance test

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

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

The photosensitive composition obtained above was coated 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. Two of these wafers were prepared, and one of them was designated as "unexposed sample". The other was set as an "exposed sample", and after irradiating a ghi ray of 100 mJ/cm ² with a ghi ray lamp ("Multi-Light" manufactured by Ushio Electric Co., Ltd.), heat treatment was performed at 140°C for 60 seconds. .

Both the "unexposed sample" and the "exposed sample" 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 the developing solution was measured, and the value obtained by dividing the difference by 60 was set as the alkali developability [ADR (Å/s)].

Evaluation of light sensitivity

The photosensitive composition obtained above was coated 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. After making the mask corresponding to the resist pattern with the line and gap ratio of 1:1 and the line width set in the range of 1~10 μm in units of 1 μm tightly attached to the wafer, use a ghi ray lamp (Ushio Electric Co., Ltd. Manufacturing "Multi-Light") was irradiated with ghi rays and heat-treated at 140°C for 60 seconds. Then, after immersing for 60 seconds in an alkali developing solution (2.38% aqueous tetramethylammonium hydroxide), it was made to dry for 60 seconds on a hot plate at 110°C.

The exposure amount (Eop exposure amount) at which the line width of 3 μm can be faithfully reproduced when the exposure amount of ghi rays is increased in units of 10 mJ/cm ² from 30 mJ/cm ² is evaluated.

Evaluation of resolution

The photosensitive composition obtained above was coated 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. A mask was placed on the obtained wafer, and 200 mJ/cm ² of ghi rays were irradiated by the same method as in the case of the above-mentioned alkali developability evaluation, and an alkali development operation was performed. The pattern state was confirmed using a laser microscope (“VK-X200” manufactured by KEYENCE Co., Ltd.), and those who could analyze with L/S=5 μm were evaluated as ○, and those who could not analyze with L/S=5 μm were evaluated as ×.

Heat resistance evaluation

The above-obtained composition for heat resistance test was coated on a 5-inch silicon wafer by a spin coater so as to have a thickness of about 1 μm, and was dried on a hot plate at 110° C. for 60 seconds. The resin component was scraped off from the obtained wafer, and its 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 at a temperature range of -100~250°C and a heating temperature of 10°C/min. conditions.

Evaluation of crack resistance

The photosensitive composition obtained above was coated on a 5-inch silicon wafer by a spin coater, and dried on a hot plate at 110° C. for 300 seconds. This coating operation was repeated to produce a wafer with a coating film thickness of 50 μm and a wafer with a coating film thickness of 100 μm. The wafer surface was observed with a laser microscope (“VK-X200” manufactured by KEYENCE Co., Ltd.), and the case where there was no crack was evaluated as ○, and the case where there was a crack was evaluated as ×.

Evaluation of softness

The photosensitive composition obtained above was applied on a polyimide film having a thickness of 50 μm using a spin coater so as to have a thickness of about 5 μm, and was dried on a hot plate at 110° C. for 300 seconds. The obtained laminated film was folded 180 degrees, and the state of the folded portion was observed using a laser microscope (“VK-X200” manufactured by KEYENCE Corporation), and the state of no cracks was evaluated as ○, and there were cracks The case was evaluated as ×.

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 according to the following points. The results are shown in Table 2.

Preparation of hardening composition

16 parts by mass of the above-mentioned phenolic hydroxyl group-containing resin and 4 parts by mass of a curing agent (“1,3,4,6-tetra(methoxymethyl) glycoluril” manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in propylene glycol monohydrate. 30 parts by mass of methyl ether acetate was filtered with a 0.2 μm membrane filter to obtain a curable composition.

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

The curable composition obtained above was coated on a 5-inch silicon wafer by a spin coater so as to have a thickness of about 1 μm, and was dried on a hot plate at 110° C. for 60 seconds. Two of these wafers were prepared, and one of them was designated as "uncured sample". The other "hardened sample" was heat-treated at 160°C for 60 seconds.

Both the "uncured sample" and the "hardened sample" 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 the developing solution was measured, and the value obtained by dividing the difference by 60 was set as the alkali developability [ADR (Å/s)].

Heat resistance rating

The curable composition obtained above was coated 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 heated at 160° C., The heat treatment was performed under the condition of 60 seconds. The resin component was scraped off from the obtained wafer, and its 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 at a temperature range of -100~250°C and a heating temperature of 10°C/min. conditions.

Cracking resistance

The curable composition obtained above was coated on a 5-inch silicon wafer by a spin coater, and dried on a hot plate at 110° C. for 300 seconds. This coating operation was repeated to produce a wafer with a coating film thickness of 50 μm and a wafer with a coating film thickness of 100 μm. The wafer surface was observed with a laser microscope (“VK-X200” manufactured by KEYENCE Co., Ltd.), and the case where there was no crack was evaluated as ○, and the case where there was a crack was evaluated as ×.

Claims (8)

A resin containing a phenolic hydroxyl group, which has a structural part (α) represented by the following structural formula (1) or (2) and a structural part (β) represented by the following structural formula (3) as repeating units, At least one of R ² , R ³ , and R ⁵ present in the resin is an aliphatic hydrocarbon group with 8 to 24 carbon atoms, and the ratio of the above-mentioned structural part (α) to the above-mentioned structural part (β) [(α) /(β)] is the range of 90/10~30/70,

(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, and 2; R ² and R ³ are independently aliphatic hydrocarbon groups, containing Any one of the hydrocarbon group, alkoxy group, and halogen atom of the aromatic ring; 1 is independently 0 or an integer of 1 to 4; m is an integer of 0 or 1 to 5; n is an integer of 0 or 1 to 7; * It is a bonding point with the benzene ring or naphthalene ring shown in the figure, and the two * may be bonded with the same aromatic ring or with different aromatic rings)

(in the formula, R ¹ is any one of a hydrogen atom, aliphatic hydrocarbon group, or a hydrocarbon group containing an aromatic ring; R ⁴ is a hydrogen atom or an aliphatic hydrocarbon group with 1 to 7 carbon atoms; R ⁵ is a hydrogen atom or a carbon atom number 8~24 aliphatic hydrocarbon group). A resin containing a phenolic hydroxyl group, which is the reaction product of the following novolak resin intermediate (M) and an alkene compound (D) having 8 to 24 carbon atoms; the novolak resin intermediate (M) is based on the following A triarylmethane type compound (A) having a molecular structure represented by the structural formula (4) or (5), a phenolic compound (B) having a phenol or an aliphatic hydrocarbon group having 1 to 7 carbon atoms, and an aldehyde compound (C) ) as the reaction raw material,

(in the formula, k is any one of 0, 1, and 2; R ² and R ³ are each independently any one of aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, alkoxy group, and halogen atom; 1 are each independently is 0 or an integer from 1 to 4; m is an integer from 0 or 1 to 5; n is an integer from 0 or 1 to 7). The phenolic hydroxyl group-containing resin according to claim 2, wherein the reaction ratio of the novolak resin intermediate (M) and the alkene compound (D) having 8 to 24 carbon atoms is the following ratio: The total mass of the above-mentioned alkene compound (D) having 8 to 24 carbon atoms is 0.5 to 30 mass quantity%. A photosensitive composition comprising the phenolic hydroxyl group-containing resin according to any one of claims 1 to 3 and a photosensitizer. A resist material using the photosensitive composition according to claim 4. A curable composition comprising the phenolic hydroxyl group-containing resin according to any one of claims 1 to 3 and a curing agent. A hardened product, which is the hardened product of the hardening composition described in claim 6. A resist material using the curable composition according to claim 6.

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