WO2020153048A1

WO2020153048A1 - Phenolic hydroxyl group-containing resin, photosensitive composition, resist film, curable composition, and cured product

Info

Publication number: WO2020153048A1
Application number: PCT/JP2019/049331
Authority: WO
Inventors: 今田　知之; 裕仁長田
Original assignee: Dic株式会社
Priority date: 2019-01-21
Filing date: 2019-12-17
Publication date: 2020-07-30
Also published as: JPWO2020153048A1; JP6940834B2; CN113348188B; KR20210093310A; TW202037626A; TWI794578B; KR102652307B1; CN113348188A

Abstract

The present invention addresses the problem of providing a phenolic hydroxyl group-containing resin having superior heat resistance and, when being used as a resist material, exhibits excellent alkali developing properties. Provided is a phenolic hydroxyl group-containing resin which is a reaction product of: an alcohol compound (X); and a novolac type phenol resin (C), of which essential reaction materials are an aliphatic aldehyde (B) and an aromatic compound (A) represented by formula (1). In formula (1): R₁ and R₂ each represent an aliphatic hydrocarbon group having 1-9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group, or a halogen atom; m, n, and p each represent an integer of 0-4; R₃ represents a hydrogen atom, an aliphatic hydrocarbon group having 1-9 carbon atoms, or a structural moiety having, on a hydrocarbon group, at least one substituent selected from alkoxy groups, halogen groups, and a hydroxyl group; and R₄ represents a hydroxyl group, an aliphatic hydrocarbon group having 1-9 carbon atoms, an alkoxy group, or a halogen atom.

Description

Phenolic hydroxyl group-containing resin, photosensitive composition, resist film, curable composition and cured product

The present invention relates to a phenolic hydroxyl group-containing resin, a photosensitive composition, a resist film, a curable composition and a cured product.

In the field of photoresists, various types of resist pattern forming methods that have been subdivided according to applications and functions are being developed one after another, and along with this, the performance requirements for resin materials for resists are becoming more sophisticated and diversified. .. For example, as a resist used in the production of semiconductors such as IC and LSI, the production of display devices such as LCD, the production of printing original plates, etc., a positive type using a photosensitizer such as an alkali-soluble resin and a 1,2-naphthoquinonediazide compound. Photoresists are known.

A positive photoresist composition using a cresol novolac epoxy resin as the alkali-soluble resin has been proposed (see, for example, Patent Documents 1 and 2).
A positive photoresist composition using a cresol novolac type epoxy resin was developed for the purpose of improving developability such as sensitivity, but in recent years, the degree of integration of semiconductors has increased and the pattern becomes finer. There is a tendency, and higher sensitivity is required. However, the positive photoresist composition using a cresol novolac epoxy resin has a problem that sufficient sensitivity for thinning cannot be obtained. Further, since various heat treatments are performed in the manufacturing process of semiconductors and the like, higher heat resistance is also required, but a positive photoresist composition using a cresol novolac epoxy resin has sufficient heat resistance. There was no problem.

Wafer level packaging technology is available for the production of patterned structures using photoresist. The wafer level packaging technology is a packaging technology for manufacturing a semiconductor package by performing resin sealing, rewiring, electrode formation in a wafer state and dicing into individual pieces.

In wafer-level packaging, as the wiring density increases, the electrochemical deposition method is used for electronic wiring (for example, see Non-Patent Document 1). The gold bumps, copper posts and copper wires used for wafer level packaging relocation require a mold of resist to be electroplated. This resist layer is very thick compared to the resist layers used in IC manufacturing. Both the size of the resist mold features and the thickness of the resist layer are, for example, 2 μm to 100 μm and it is necessary to pattern the photoresist with a high aspect ratio (resist thickness to line size).

Regarding patterning of photoresist with high aspect ratio, it has been proposed to use an aliphatic polyaldehyde as a knotting agent for meta-cresol or para-cresol when synthesizing a novolac resin (see, for example, Patent Document 3). However, there is a problem that it is difficult to satisfy both the heat resistance and the alkali dissolution rate, which are important properties as a thick film resist.

JP, 2008-0881197, A JP, 2002-107925, A Japanese Unexamined Patent Publication No. 9-6003

The problem to be solved by the present invention is to provide a phenolic hydroxyl group-containing resin having high heat resistance and exhibiting excellent alkali developability when used as a resist material.

As a result of intensive studies to solve the above problems, the present inventors have found that a part or all of the carboxyl groups in the reaction product is a reaction product of a triaryl compound containing a carboxyl group and an aliphatic aldehyde. The inventors have found that a phenolic hydroxyl group-containing resin esterified with an alcohol compound has excellent heat resistance and alkali developability, and completed the present invention.

That is, the present invention relates to a novolac type phenolic resin (C) and an alcohol compound (X), which use an aromatic compound (A) represented by the following formula (1) and an aliphatic aldehyde (B) as essential reaction raw materials. The present invention relates to a phenolic hydroxyl group-containing resin which is a reaction product of

(In the formula (1), R ₁ and R ₂ each independently represent an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group or a halogen atom.
m, n and p each independently represent an integer of 0-4.
When R ₁ is a plurality, the plurality of R ₁ may be the same or different.
When R ₂ are a plurality, the plurality of R ₂ may be the same or different.
R ₃ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural moiety having at least one substituent selected from an alkoxy group, a halogen group and a hydroxyl group on the hydrocarbon group.
R ₄ represents a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group or a halogen atom.
If R ₄ is plural, R ₄ may be the same or different. )

According to the present invention, a phenolic hydroxyl group-containing resin having high heat resistance and exhibiting excellent alkali developability when used as a resist material can be provided.

FIG. 3 is a view showing a GPC chart of a carboxylic acid-containing phenolic trinuclear compound (A-1). FIG. 3 is a diagram showing a ¹³ C-NMR chart of a carboxylic acid-containing phenolic trinuclear compound (A-1). It is a figure which shows the GPC chart of a novolac type phenol resin (C-1). It is a figure which shows the ¹³ C-NMR chart of a novolac type phenol resin (C-1). It is a figure which shows the GPC chart of esterified novolac type phenol resin (Z-1). FIG. 3 is a diagram showing a ¹³ C-NMR chart of an esterified novolac type phenolic resin (Z-1). It is a figure which shows the GPC chart of esterified novolac type phenol resin (Z-2). FIG. 3 is a diagram showing a ¹³ C-NMR chart of an esterified novolac type phenol resin (Z-2). It is a figure which shows the GPC chart of esterified novolak type phenol resin (Z-3). FIG. 3 is a diagram showing a ¹³ C-NMR chart of an esterified novolac type phenol resin (Z-3). It is a figure which shows the GPC chart of a novolak resin (C'-2). It is a figure which shows the GPC chart of a novolak resin (C'-3).

An embodiment of the present invention will be described below. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within a range that does not impair the effects of the present invention.

[Phenolic hydroxyl group-containing resin]
The phenolic hydroxyl group-containing resin of the present invention is a novolac-type phenol resin (C) and an alcohol compound, which contain an aromatic compound (A) represented by the following formula (1) and an aliphatic aldehyde (B) as essential reaction raw materials. It is a reaction product with (X).

The phenolic hydroxyl group-containing resin of the present invention has a triarylmethane structure. Since the aromatic ring is contained at a high density by having the triarylmethane structure, the phenolic hydroxyl group-containing resin of the present invention has extremely high heat resistance.
In the triarylmethane structure of the above formula (1), two hydroxy groups and a carboxyl group are substituted by different aromatic rings, and a strong hydrogen bond is not formed. As a result, the phenolic hydroxyl group-containing resin of the present invention can maintain good proton dissociation properties and exhibit excellent alkali developability. In addition, since some or all of the carboxyl groups in the triarylmethane structure are esterified by the reaction with the alcohol compound (X), the polarities before and after the hydrolysis of the ester group (before and after the carboxyl group formation) are extremely polar. Can be induced, and good development contrast can be obtained.

[Novolak type phenolic resin]
The novolac type phenol resin (C) is a resin in which an aromatic compound (A) represented by the following formula (1) and an aliphatic aldehyde (B) are essential reaction raw materials.

In the above formula (1), the aliphatic hydrocarbon group having 1 to 9 carbon atoms represented by R ₁ , R ₂ , R ₃ and R ₄ is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, t Examples thereof include an alkyl group having 1 to 9 carbon atoms and a cycloalkyl group having 3 to 9 carbon atoms such as a butyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group and a nonyl group.

In the formula (1), examples of the alkoxy group represented by R ₁ , R ₂ and R ₄ include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group and a cyclohexyloxy group.

In the formula (1), examples of the aryl group represented by R ₁ and R ₂ include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and an anthryl group.

In the formula (1), examples of the aralkyl group represented by R ₁ and R ₂ include a benzyl group, a phenylethyl group, a phenylpropyl group, and a naphthylmethyl group.

In the formula (1), examples of the halogen atom represented by R ₁ , R ₂ and R ₄ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the above formula (1), “a structural moiety having at least one substituent selected from an alkoxy group, a halogen group and a hydroxyl group on the hydrocarbon group” of R ₃ is a halogenated alkyl group, a halogenated aryl group, 2 Examples thereof include an alkoxyalkoxy group such as a -methoxyethoxy group and a 2-ethoxyethoxy group, and an alkylalkoxy group substituted with a hydroxy group.

In the above formula (1), m and n are each preferably an integer of 2 or 3.
When m and n are each 2, 2 R ₁ and 2 R ₂ are preferably each independently an alkyl group having 1 to 3 carbon atoms. At this time, two R ₁ and two R ₂ are preferably bonded to the 2,5-position of the phenolic hydroxyl group, respectively.

In the above formula (1), p is preferably an integer of 0, 1 or 2.

As the aromatic compound (A) represented by the formula (1), those having the same structure may be used alone, or a plurality of compounds having different molecular structures may be used.

The aromatic compound (A) represented by the above formula (1) can be prepared, for example, by a condensation reaction between an alkyl-substituted phenol (a1) and an aromatic aldehyde (a2) having a carboxyl group.
The aromatic compound (A) represented by the above formula (1) can be prepared, for example, by a condensation reaction of an alkyl-substituted phenol (a1) and an aromatic ketone (a3) having a carboxyl group.

The alkyl-substituted phenol (a1) is a phenol substituted with an alkyl group, and examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms, and a methyl group is preferable.
Specific examples of the alkyl-substituted phenol (a1) include o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, p-octylphenol, pt-butylphenol, o. -Monoalkylphenols such as cyclohexylphenol, m-cyclohexylphenol and p-cyclohexylphenol; dialkyl such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,4-xylenol and 2,6-xylenol Alkylphenol; trialkylphenols such as 2,3,5-trimethylphenol, 2,3,6-trimethylphenol and the like are listed. Among these, dialkylphenol is preferable, and 2,5-xylenol and 2,6-xylenol are more preferable.
The alkyl-substituted phenol (a1) may be used alone or in combination of two or more.

Examples of the aromatic aldehyde (a2) having a carboxyl group include a compound having a formyl group on the benzene ring such as benzene, phenol and resorcin, and a compound having an alkyl group, an alkoxy group, a halogen atom and the like in addition to the formyl group. ..
Specific examples of the aromatic aldehyde (a2) having a carboxyl group include 4-formylbenzoic acid, 2-formylbenzoic acid, 3-formylbenzoic acid, methyl 4-formylbenzoate, ethyl 4-formylbenzoate, 4- Propyl formyl benzoate, isopropyl 4-formyl benzoate, butyl 4-formyl benzoate, isobutyl 4-formyl benzoate, tertiary butyl 4-formyl benzoate, cyclohexyl 4-formyl benzoate, tertiary octyl benzoyl benzoate Etc. Of these, 4-formylbenzoic acid is preferable.
The aromatic aldehyde (a2) having a carboxyl group may be used alone or in combination of two or more.

The aromatic ketone (a3) having a carboxyl group is a compound having at least one carboxyl group and carbonyl group in the aromatic ring.
Specific examples of the aromatic ketone (a3) having a carboxyl group include, for example, 2-acetylbenzoic acid, 3-acetylbenzoic acid, 4-acetylbenzoic acid, methyl 2-acetylbenzoate, and ethyl 2-acetylbenzoate. Propyl 2-acetylbenzoate, Isopropyl 2-acetylbenzoate, Butyl 2-acetylbenzoate, Isobutyl 2-acetylbenzoate, Tertiary butyl 2-acetylbenzoate, Cyclohexyl 2-acetylbenzoate, 2-Acetylbenzoic acid Examples include tertiary octyl. Of these, 2-acetylbenzoic acid and 4-acetylbenzoic acid are preferable.
The aromatic ketone (a3) may be used alone or in combination of two or more.

Specific examples of the aliphatic aldehyde (B) include formaldehyde, paraformaldehyde, 1,3,5-trioxane, acetaldehyde, propionaldehyde, tetraoxymethylene, polyoxymethylene, chloral, hexamethylenetetramine, glyoxal, n-butyraldehyde. , Caproaldehyde, allyl aldehyde, crotonaldehyde, acrolein and the like.
As the aliphatic aldehyde compound (B), one type may be used alone, or two or more types may be used in combination.

The aliphatic aldehyde (B) is preferably one or more selected from formaldehyde and paraformaldehyde, more preferably formaldehyde.
When formaldehyde and an aliphatic aldehyde other than formaldehyde are used as the aliphatic aldehyde (B), the amount of the aliphatic aldehyde other than formaldehyde used is in the range of 0.05 to 1 mol per 1 mol of formaldehyde. It is preferable.

The method for producing the novolac type phenolic resin (C) preferably includes the following three steps 1 to 3 (step 1)
By heating the alkyl-substituted phenol (a1) and the aromatic aldehyde having a carboxyl group (a2) in the presence of an acid catalyst, if necessary, using a solvent in the range of 60 to 140° C. to perform polycondensation, An aromatic compound (A) is obtained.
(Process 2)
The aromatic compound (A) obtained in step 1 is isolated from the reaction solution.
(Process 3)
Aromatic compound (A) and aliphatic aldehyde (B) isolated in step 2 are heated in the range of 60 to 140° C. in the presence of an acid catalyst and, if necessary, a solvent to be polycondensed. Thus, a novolac type phenol resin (C) is obtained.

Examples of the acid catalyst used in the above step 1 and step 3 include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, manganese acetate and the like. These acid catalysts may be used alone or in combination of two or more. Among these acid catalysts, sulfuric acid and p-toluenesulfonic acid are preferable in Step 1, and sulfuric acid, oxalic acid and zinc acetate are preferable in Step 3 from the viewpoint of excellent activity. The acid catalyst may be added before the reaction or during the reaction.

Examples of the solvent used as necessary in the above step 1 and step 3 include monoalcohols such as methanol, ethanol and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butane. Polyols such as diol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol and glycerin 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether, etc. Glycol ethers; cyclic ethers such as 1,3-dioxane and 1,4-dioxane; glycol esters such as ethylene glycol acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene. Can be mentioned. These solvents may be used alone or in combination of two or more. Among these solvents, 2-ethoxyethanol is preferable from the viewpoint of excellent solubility of the obtained compound.

The charging ratio [(a1)/(a2)] of the alkyl-substituted phenol (a1) to the aromatic aldehyde (a2) having a carboxyl group in the step 1 is such that the unreacted alkyl-substituted phenol (a1) can be removed and the product can be removed. The molar ratio is preferably in the range of 1/0.2 to 1/0.5, and more preferably in the range of 1/0.25 to 1/0.45, because the yield and the purity of the reaction product are excellent.

The charging ratio [(A)/(B)] of the aromatic compound (A) and the aliphatic aldehyde (B) in step 3 can suppress excessive high molecular weight (gelation) and is suitable as a phenol resin for resist. The molar ratio is preferably in the range of 1/0.5 to 1/1.2, and more preferably in the range of 1/0.6 to 1/0.9, since a high molecular weight is obtained.

As the method for isolating the aromatic compound (A) from the reaction solution in step 2, for example, a precipitate obtained by adding the reaction solution to a poor solvent (S1) in which the reaction product is insoluble or sparingly soluble After filtering off, the reaction product is dissolved and dissolved in a solvent (S2) which is also miscible with the poor solvent (S1), and the solution is added again to the poor solvent (S1), and the resulting precipitate is filtered off. To be
Examples of the poor solvent (S1) used in this case include water; monoalcohols such as methanol, ethanol and propanol; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane and cyclohexane; toluene and xylene. And other aromatic hydrocarbons. Among these poor solvents (S1), water and methanol are preferable because they can simultaneously remove the acid catalyst efficiently. On the other hand, examples of the solvent (S2) include monoalcohols such as methanol, ethanol, propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, polyols such as glycerin; 2-ethoxyethanol, Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether; Examples thereof include cyclic ethers such as 3-dioxane and 1,4-dioxane; glycol esters such as ethylene glycol acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. When water is used as the poor solvent (S1), acetone is preferable as the (S2). The poor solvent (S1) and the solvent (S2) may be used alone or in combination of two or more.

When aromatic hydrocarbons such as toluene and xylene are used as the solvent in the above step 1 and step 3, if heated at 80° C. or higher, the aromatic compound (A) produced by the reaction is dissolved in the solvent. By cooling as it is, crystals of the aromatic compound (A) are precipitated, and thus the aromatic compound (A) can be isolated by filtering this. In this case, the poor solvent (S1) and the solvent (S2) may not be used.

The aromatic compound (A) represented by the above formula (1) can be obtained by the isolation method of the above step 2.
The purity of the aromatic compound (A) is preferably 90% or higher, more preferably 94% or higher, and more preferably 98% or higher, as calculated from the gel permeation chromatography (GPC) chart. Is particularly preferable. The purity of the aromatic compound (A) can be obtained from the area ratio in the GPC chart and is measured under the measurement conditions described later.

The weight average molecular weight (Mw) of the novolac type phenol resin (C) is preferably in the range of 2,000 to 35,000, more preferably in the range of 2,000 to 25,000.
The weight average molecular weight (Mw) of the novolac type phenol resin (C) is measured by gel permeation chromatography (hereinafter abbreviated as “GPC”) under the following measurement conditions.

(GPC measurement conditions)
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation
Column: Showa Denko KK "Shodex KF802" (8.0mmΦ×300mm)
+ Showa Denko KK "Shodex KF802" (8.0mmφ300mm)
+ Showa Denko KK "Shodex KF803" (8.0mmΦ×300mm)
+ Showa Denko KK "Shodex KF804" (8.0mmΦ×300mm)
Column temperature: 40°C
Detector: RI (differential refractometer)
Data processing: "GPC-8020 model II version 4.30" manufactured by Tosoh Corporation
Developing solvent: Tetrahydrofuran Flow rate: 1.0 mL/min Sample: 0.5% by mass of tetrahydrofuran solution in terms of resin solid content filtered with a microfilter (100 μl)
Standard sample: Monodisperse polystyrene below

(Standard sample: monodisperse polystyrene)
Tosoh Corporation "A-500"
Tosoh Corporation "A-2500"
Tosoh Corporation “A-5000”
Tosoh Corporation "F-1"
Tosoh Corporation "F-2"
Tosoh Corporation "F-4"
Tosoh Corporation “F-10”
Tosoh Corporation “F-20”

[Alcohol compound (X)]
The phenolic hydroxyl group-containing resin of the present invention is a reaction product of a novolac type phenol resin (C) and an alcohol compound (X). Here, the reaction between the novolac type phenol resin (C) and the alcohol compound (X) is, for example, a dehydration esterification reaction.

Examples of the alcohol compound (X) include the number of carbon atoms of methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, propylene glycol, trimethylolpropane, etc. Aliphatic alcohols having 10 or less; aromatic alcohols having 10 or less carbon atoms such as benzyl alcohol; 2-methoxyethyl alcohol, 2-ethoxyethyl alcohol, 1-methoxy-2-propyl alcohol, 1-ethoxy-2-propyl alcohol Ether ethers having 10 or less carbon atoms containing an ether bond, such as 3-methoxy-1-butyl alcohol and 2-isopropoxyethyl alcohol; 10-carbon atoms or less containing a ketone group, such as 3-hydroxy-2-butanone Examples thereof include keto alcohol; ester alcohols having an ester group and having 10 or less carbon atoms, such as methyl hydroxyisobutyrate. Of these, aliphatic alcohols having 10 or less carbon atoms and ether alcohols having 10 or less carbon atoms are preferable, and ethyl alcohol, n-propyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, isobutyl alcohol (2 -Methyl-2-propanol), t-butyl alcohol and 2-ethoxyethyl alcohol (2-ethoxyethanol) are more preferable.
The alcohol compound (X) may be used alone or in combination of two or more.

The dehydration esterification reaction can be performed by stirring a mixture of the novolac type phenol resin (C) and the alcohol compound (X) in the presence of an acid catalyst.
Examples of the acid catalyst include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate and manganese acetate. These acid catalysts may be used alone or in combination of two or more.
The reaction temperature is not particularly limited, but may be, for example, in the range of 10° C. to 60° C., and room temperature is preferable because no special device is required.

The dehydration esterification reaction of the novolac type phenol resin (C) and the alcohol compound (X) is carried out by reacting with the carboxyl group in the novolac type phenol resin (C) derived from the aromatic compound (A) represented by the formula (1). The alcohol compound (X) reacts to form an ester bond with dehydration.
In the dehydration esterification reaction, the charging ratio of the novolac type phenol resin (C) and the alcohol compound (X) is not particularly limited, but for example, the weight ratio is phenol resin/alcohol=1/0.5 to 1/10. ..

The phenolic hydroxyl group-containing resin of the present invention is a resin containing a structure in which a part or all of the carboxyl groups of the novolac type phenol resin (C) are esterified, and the esterification rate of the carboxyl groups of the novolac type phenol resin (C). Is preferably 5 to 90 mol %, more preferably 10 to 85 mol% or 5 to 70 mol %.
The esterification rate of the phenolic hydroxyl group-containing resin of the present invention is confirmed by the method described in Examples.

The number average molecular weight (Mn) of the phenolic hydroxyl group-containing resin of the present invention is preferably in the range of 500 to 7,000, more preferably in the range of 1,000 to 5,000.
The weight average molecular weight (Mw) of the phenolic hydroxyl group-containing resin of the present invention is preferably in the range of 3,000 to 20,000, more preferably in the range of 5,000 to 15,000.
The number average molecular weight and the weight average molecular weight of the phenolic hydroxyl group-containing resin of the present invention are the same as those of the novolac type phenol resin (C), and are measured by gel permeation chromatography (hereinafter abbreviated as “GPC”).

[Photosensitive composition]
The photosensitive composition of the present invention contains the phenolic hydroxyl group-containing resin of the present invention and a photoacid generator.
The photo-acid generator is not particularly limited, and known photo-acid generators can be used, and examples thereof include organic halogen compounds, sulfonic acid esters, onium salts, diazonium salts, and disulfone compounds.

The following are specific examples of the photo-acid generator.
Tris(trichloromethyl)-s-triazine, tris(tribromomethyl)-s-triazine, tris(dibromomethyl)-s-triazine, 2,4-bis(tribromomethyl)-6-p-methoxyphenyl-s A haloalkyl group-containing s-triazine derivative such as triazine, (2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine);

Halogen-substituted paraffinic hydrocarbon compounds such as 1,2,3,4-tetrabromobutane, 1,1,2,2-tetrabromoethane, carbon tetrabromide and iodoform; hexabromocyclohexane, hexachlorocyclohexane, hexabromocyclo Halogen-substituted cycloparaffinic hydrocarbon compounds such as dodecane;

Haloalkyl group-containing benzene derivatives such as bis(trichloromethyl)benzene and bis(tribromomethyl)benzene; haloalkyl group-containing sulfone compounds such as tribromomethylphenyl sulfone and trichloromethylphenyl sulfone; halogen containing 2,3-dibromosulfolane and the like Sulfolane compounds; haloalkyl group-containing isocyanurate compounds such as tris(2,3-dibromopropyl) isocyanurate;

Triphenylsulfonium chloride, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroacene Sulfonate, triphenylsulfonium hexafluorophosphonate, and other sulfonium salts;

Iodonium salts such as diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphonate;

Methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, phenyl p-toluenesulfonate, 1,2,3-tris(p-toluenesulfonyloxy)benzene, benzoin p-toluenesulfonate Ester, methyl methanesulfonate, ethyl methanesulfonate, butyl methanesulfonate, 1,2,3-tris(methanesulfonyloxy)benzene, phenyl methanesulfonate, benzoin methanesulfonate ester, methyl trifluoromethanesulfonate, trifluoromethane Sulfonate compounds such as ethyl sulfonate, butyl trifluoromethanesulfonate, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, phenyl trifluoromethanesulfonate and benzoin ester trifluoromethanesulfonate; disulfone compounds such as diphenyldisulfone ;

Bis(phenylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, cyclohexylsulfonyl-(2-methoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(3-methoxyphenylsulfonyl)diazomethane, Cyclohexylsulfonyl-(4-methoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2-methoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(3-methoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(4-methoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl -(2-Fluorophenylsulfonyl)diazomethane, cyclohexylsulfonyl-(3-fluorophenylsulfonyl)diazomethane, cyclohexylsulfonyl-(4-fluorophenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2-fluorophenylsulfonyl)diazomethane, cyclopentylsulfonyl-( 3-fluorophenylsulfonyl)diazomethane, cyclopentylsulfonyl-(4-fluorophenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2-chlorophenylsulfonyl)diazomethane, cyclohexylsulfonyl-(3-chlorophenylsulfonyl)diazomethane, cyclohexylsulfonyl-(4-chlorophenylsulfonyl) ) Diazomethane, cyclopentylsulfonyl-(2-chlorophenylsulfonyl)diazomethane, cyclopentylsulfonyl-(3-chlorophenylsulfonyl)diazomethane, cyclopentylsulfonyl-(4-chlorophenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2-trifluoromethylphenylsulfonyl)diazomethane, Cyclohexylsulfonyl-(3-trifluoromethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(4-trifluoromethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2-trifluoromethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(3-trifluoro Methylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(4-trifluoromethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2- Trifluoromethoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(3-trifluoromethoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(4-trifluoromethoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2-trifluoromethoxyphenylsulfonyl)diazomethane, Cyclopentylsulfonyl-(3-trifluoromethoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(4-trifluoromethoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2 3,4-Trimethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2,4,6-triethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2,3,4-triethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2,4, 6-trimethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2,4,6-triethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2,3,4- Triethylphenylsulfonyl)diazomethane, phenylsulfonyl-(2-methoxyphenylsulfonyl)diazomethane, phenylsulfonyl-(3-methoxyphenylsulfonyl)diazomethane, phenylsulfonyl-(4-methoxyphenylsulfonyl)diazomethane, bis(2-methoxyphenylsulfonyl) Diazomethane, bis(3-methoxyphenylsulfonyl)diazomethane, bis(4-methoxyphenylsulfonyl)diazomethane, phenylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane, phenylsulfonyl-(2,3,4-trimethylphenyl Sulfonyl)diazomethane, phenylsulfonyl-(2,4,6-triethylphenylsulfonyl)diazomethane, phenylsulfonyl-(2,3,4-triethylphenylsulfonyl)diazomethane, 2,4-dimethylphenylsulfonyl-(2,4,6 -Trimethylphenylsulfonyl)diazomethane, 2,4-dimethylphenylsulfonyl-(2,3,4-trimethylphenylsulfonyl) ) Sulfondiazide compounds such as diazomethane, phenylsulfonyl-(2-fluorophenylsulfonyl)diazomethane, phenylsulfonyl-(3-fluorophenylsulfonyl)diazomethane, phenylsulfonyl-(4-fluorophenylsulfonyl)diazomethane and the like;

O-nitrobenzyl ester compounds such as o-nitrobenzyl-p-toluenesulfonate;

Sulfone hydrazide compounds such as N,N'-di(phenylsulfonyl)hydrazide;

A sulfonium salt which is a salt of a sulfonium cation such as triarylsulfonium or triaralkylsulfonium and a sulfonate such as fluoroalkane sulfonate, arene sulfonate or alkane sulfonate;

An iodonium salt that is a salt of an iodonium cation such as diaryliodonium and a sulfonate such as fluoroalkane sulfonate, arene sulfonate, or alkane sulfonate;

Bissulfonyldiazomethane compounds such as bis(alkylsulfonyl)diazomethane, bis(cycloalkylsulfonyl)diazomethane, bis(perfluoroalkylsulfonyl)diazomethane, bis(arylsulfonyl)diazomethane, bis(aralkylsulfonyl)diazomethane;

An N-sulfonyloxyimide compound comprising a combination of a dicarboxylic acid imide compound and a sulfonate such as fluoroalkane sulfonate, arene sulfonate, and alkane sulfonate;

Benzoin sulfonate compounds such as benzoin tosylate, benzoin mesylate, benzoin butane sulfonate;

A polyhydroxyarene sulfonate compound in which all the hydroxy groups of the polyhydroxyarene compound are replaced with sulfonates such as fluoroalkane sulfonate, arene sulfonate, and alkane sulfonate;

Nitrobenzyl sulfonate compounds such as (poly)nitrobenzyl fluoroalkane sulfonate, (poly)nitrobenzyl arene sulfonate, (poly)nitrobenzyl alkane sulfonate;
Fluoroalkanebenzyl sulfonate compounds such as (poly)fluoroalkanebenzyl fluoroalkanesulfonate, (poly)fluoroalkanebenzyl arenesulfonate, and (poly)fluoroalkanebenzyl alkanesulfonate;

Bis(arylsulfonyl)alkane compound;

Bis-O-(arylsulfonyl)-α-dialkylglyoxime, bis-O-(arylsulfonyl)-α-dicycloalkylglyoxime, bis-O-(arylsulfonyl)-α-diarylglyoxime, bis-O -(Alkylsulfonyl)-α-dialkylglyoxime, bis-O-(alkylsulfonyl)-α-dicycloalkylglyoxime, bis-O-(alkylsulfonyl)-α-diarylglyoxime, bis-O-(fluoro Alkylsulfonyl)-α-dialkylglyoxime, bis-O-(fluoroalkylsulfonyl)-α-dicycloalkylglyoxime, bis-O-(fluoroalkylsulfonyl)-α-diarylglyoxime, bis-O-(aryl Sulfonyl)-α-dialkylnioxime, bis-O-(arylsulfonyl)-α-dicycloalkylnioxime, bis-O-(arylsulfonyl)-α-diarylnioxime, bis-O-(alkylsulfonyl)- α-dialkylnioxime, bis-O-(alkylsulfonyl)-α-dicycloalkylnioxime, bis-O-(alkylsulfonyl)-α-diarylnioxime, bis-O-(fluoroalkylsulfonyl)-α- Oxime compounds such as dialkyl nioximes, bis-O-(fluoroalkylsulfonyl)-α-dicycloalkyl nioximes, bis-O-(fluoroalkylsulfonyl)-α-diaryl nioximes;

Arylsulfonyloxyiminoarylacetonitrile, alkylsulfonyloxyiminoarylacetonitrile, fluoroalkylsulfonyloxyiminoarylacetonitrile, ((arylsulfonyl)oxyimino-thiophene-ylidene)arylacetonitrile, ((alkylsulfonyl)oxyimino-thiophene-ylidene)arylacetonitrile, ((Fluoroalkylsulfonyl)oxyimino-thiophene-ylidene)arylacetonitrile, bis(arylsulfonyloxyimino)arylene diacetonitrile, bis(alkylsulfonyloxyimino)arylene diacetonitrile, bis(fluoroalkylsulfonyloxyimino)arylene diacetonitrile, aryl Modified oxime compounds such as fluoroalkanone-O-(alkylsulfonyl)oxime, arylfluoroalkanone-O-(arylsulfonyl)oxime and arylfluoroalkanone-O-(fluoroalkylsulfonyl)oxime.

The photo-acid generator may be used alone or in combination of two or more.
The content of the photo-acid generator in the photosensitive composition of the present invention is, for example, in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin solid content in the photosensitive composition, and preferably The range is 0.1 parts by mass to 10 parts by mass.
When the content of the photo-acid generator is within the above range, the photosensitive composition of the present invention can be a photosensitive composition having high photosensitivity.

The photosensitive composition of the present invention may contain the phenolic hydroxyl group-containing resin of the present invention and the photo-acid generator, and may optionally contain other components.
Examples of the other components include organic base compounds, resins other than the phenolic hydroxyl group-containing resin of the present invention, photosensitizers, surfactants, dyes, fillers, crosslinking agents, and dissolution accelerators.

The photosensitive composition of the present invention may contain an organic base compound for neutralizing the acid generated from the photoacid generator during exposure. When the photosensitive composition of the present invention contains the organic base compound, it is possible to obtain the effect of preventing the dimensional variation of the resist pattern due to the movement of the acid generated from the photo-acid generator.

Specific examples of the organic base compound include pyrimidine, (poly)aminopyrimidine, (poly)hydroxypyrimidine, (poly)amino(poly)hydroxypyrimidine, (poly)amino(poly)alkylpyrimidine, (poly)amino(poly) ) Pyrimidine compounds such as alkoxypyrimidine, (poly)hydroxy(poly)alkylpyrimidine and (poly)hydroxy(poly)alkoxypyrimidine; pyridine compounds such as pyridine, (poly)alkylpyridine and dialkylaminopyridine; polyalkanolamine, tri( Hydroxyalkyl group-containing amine compounds such as hydroxyalkyl)aminoalkane and bis(hydroxyalkyl)iminotris(hydroxyalkyl)alkane; aminoaryl compounds such as aminophenol.
The organic base compounds may be used alone or in combination of two or more.

The content of the organic base compound in the photosensitive composition of the present invention is preferably in the range of 0.1 to 100 mol% and preferably 1 to 50 mol% with respect to 1 mol of the photoacid generator. The range is more preferable.

The photosensitive composition of the present invention may contain a resin other than the phenolic hydroxyl group-containing resin of the present invention.
The other resin is not particularly limited and is, for example, a resin soluble in an alkali developing solution or a resin soluble in an alkaline developing solution when used in combination with an additive such as a photo-acid generator.

Examples of the other resins include phenol resins other than the phenolic hydroxyl group-containing resin of the present invention; p-hydroxystyrene, p-(1,1,1,3,3,3-hexafluoro-2-hydroxypropyl)styrene, etc. Of the hydroxy group-containing styrene compound homopolymer or copolymer; the hydroxyl group of the phenol resin or the hydroxy group-containing styrene compound polymer is modified with an acid-decomposable group such as t-butoxycarbonyl group or benzyloxycarbonyl group. Resins; homopolymers or copolymers of (meth)acrylic acid; alternating polymers of alicyclic polymerizable monomers such as norbornene compounds and tetracyclododecene compounds, and maleic anhydride or maleimide.

Specific examples of the phenolic resin other than the phenolic hydroxyl group-containing resin of the present invention include phenol novolac resins, cresol novolac resins, naphthol novolac resins, cocondensed novolac resins using various phenolic compounds, and aromatic hydrocarbon formaldehyde resins. Modified phenol resin, dicyclopentadienephenol addition type resin, phenol aralkyl resin (Zyloc resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, biphenyl modified phenol resin (polyphenol nucleus linked with bismethylene group (Hydric phenol compound), biphenyl modified naphthol resin (polyhydric naphthol compound in which phenol nucleus is linked by bismethylene group), aminotriazine modified phenolic resin (polyhydric phenol compound in which phenol nucleus is linked by melamine, benzoguanamine, etc.) and alkoxy group Examples thereof include phenol resins such as an aromatic ring-containing modified novolac resin (a polyvalent phenol compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).

Among the specific examples of the phenolic resin other than the phenolic hydroxyl group-containing resin of the present invention, a cresol novolak resin, and cresol and other phenols are obtained because the photosensitive composition has an excellent balance of developability, heat resistance and fluidity. A co-contracting novolak resin with a polar compound is preferred.
The cresol novolac resin or the co-condensed novolac resin of cresol and other phenolic compound is specifically an essential reaction of one or more cresols selected from o-cresol, m-cresol and p-cresol with an aldehyde compound. It is a novolak resin obtained by using, as a raw material, other phenolic compounds in combination.

The other resins may be used alone or in combination of two or more.
The content of the other resin in the photosensitive composition of the present invention is not particularly limited and may be arbitrarily set depending on the desired use. For example, the proportion of the phenolic hydroxyl group-containing resin of the present invention in the total resin components in the photosensitive composition of the present invention may be set to 60% by mass or more, and preferably 80% by mass or more.

The photosensitive composition of the present invention may contain a photosensitizer usually used for resist materials. The photosensitizer is, for example, a compound having a quinonediazide group.
Specific examples of the compound having a quinonediazide group include an ester compound or an amidated product of an aromatic (poly)hydroxy compound and a sulfonic acid compound having a quinonediazide group. The ester compound also includes a partial ester compound, and the amidation product includes a partial amidation product.

Specific examples of the sulfonic acid compound having a quinonediazide group include naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, orthoanthraquinonediazidesulfonic acid, 1,2- Examples thereof include naphthoquinone-2-diazide-5-sulfonic acid.
As a specific example of the sulfonic acid compound having a quinonediazide group, a halide further substituted with halogen can be used.

Examples of the aromatic (poly)hydroxy compound include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone and 2,3,6- Trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4',6-pentahydroxybenzophenone,2,2',3,4,4'-pentahydroxybenzophenone,2,2',3,4,5-pentahydroxybenzophenone,2,3',4 Polyhydroxybenzophenone compounds such as 4′,5′,6-hexahydroxybenzophenone and 2,3,3′,4,4′,5′-hexahydroxybenzophenone;
Bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,2 4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl) Propane, 4,4'-{1-[4-[2-(4-hydroxyphenyl)-2-propyl]phenyl]ethylidene}bisphenol, 3,3'-dimethyl-{1-[4-[2-( Bis[(poly)hydroxyphenyl]alkane compounds such as 3-methyl-4-hydroxyphenyl)-2-propyl]phenyl]ethylidene}bisphenol;
Tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethyl) A tris(hydroxyphenyl)methane compound such as phenyl)-3,4-dihydroxyphenylmethane or bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane or a methyl-substituted compound thereof;
Bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-4- Hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis( 5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-) 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- Bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methane compounds such as 4-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane and the like Examples thereof include methyl substitution products.

The photosensitizers may be used alone or in combination of two or more.
The content of the photosensitizer in the photosensitive composition of the present invention is 5 to 50 based on 100 parts by mass of the total resin component of the photosensitive composition of the present invention, since the photosensitive composition has excellent photosensitivity. It is preferably part by mass.

The photosensitive composition of the present invention may contain a surfactant. When the photosensitive composition of the present invention contains a surfactant, when the photosensitive composition of the present invention is used for a resist, effects such as improvement of film-forming property and pattern adhesion, reduction of development defects, etc. Is obtained.
A known surfactant can be used as the surfactant. Examples of the surfactant include nonionic surfactants, fluorine-based surfactants, silicone-based surfactants, and the like.

The surfactants may be used alone or in combination of two or more.
The content of the surfactant in the photosensitive composition of the present invention is preferably 0.001 to 2 parts by mass based on 100 parts by mass of the total resin components of the photosensitive composition of the present invention.

The photosensitive composition of the present invention is preferably prepared by dissolving the phenolic hydroxyl group-containing resin of the present invention in an organic solvent.
Examples of the organic solvent include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether propylene glycol monomethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diether. Dialkylene glycol dialkyl ethers such as propyl ether and diethylene glycol dibutyl ether; alkylene glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; acetone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone, etc. Ketone compound; cyclic ether such as dioxane; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2-hydroxy-3- Examples thereof include ester compounds such as methyl methyl butanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate and ethyl acetoacetate.

The organic solvent may be used alone or in combination of two or more.
The content of the organic solvent in the photosensitive composition of the present invention is not particularly limited, and may be set, for example, to an amount that can dissolve all the phenolic hydroxyl group-containing resin of the present invention in the photosensitive composition.

The photosensitive composition of the present invention can be produced by blending the above components and mixing them using a stirrer or the like. When the photosensitive composition of the present invention contains a filler or a pigment, it can be manufactured by dispersing or mixing using a dispersing device such as a dissolver, a homogenizer, or a three roll mill.

The photosensitive composition of the present invention can be used as a resist material.
When the photosensitive composition of the present invention is used as a resist material, the photosensitive composition of the present invention may be used as it is as a coating material, or may be obtained by applying the photosensitive composition of the present invention onto a support film. The coating film may be desolvated to obtain a resist film.
Examples of the support film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. The support film may be a single layer film or a laminated film composed of a plurality of films. The surface of the support film may be corona-treated or coated with a release agent.

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

When the photosensitive composition of the present invention is used for a permanent resist film, it may contain a crosslinking agent.
Examples of the cross-linking agent include those similar to the curing agent contained in the curable composition described below.
The crosslinking agents may be used alone or in combination of two or more.

Examples of the method for forming the resist permanent film include the following methods.
First, the photosensitive composition of the present invention is applied onto an object to be subjected to photolithography such as a silicon substrate, a silicon carbide substrate, a gallium nitride substrate, and prebaked at a temperature condition of 60 to 150°C. The coating method is the same as that described above. Next, the resist pattern is formed by exposing through the resist pattern, thermally curing it at a temperature condition of 110 to 210° C., and then developing with an alkali developing solution. Alternatively, after the exposure, it may be first developed with an alkali developing solution and then thermally cured under a temperature condition of 110 to 210°C.

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

[Curable composition]
The curable composition of the present invention contains the phenolic hydroxyl group-containing resin of the present invention and a curing agent.
The curing agent 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, for example, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, a resole resin, an epoxy compound, an isocyanate. Examples thereof include compounds, compounds containing double bonds such as azide compounds and alkenyl ether groups, acid anhydrides, and oxazoline compounds.

Examples of the melamine compound include hexamethylolmelamine, hexamethoxymethylmelamine, a compound in which 1 to 6 methylol groups of hexamethylolmelamine are methoxymethylated, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, and hexamethylolmelamine. Examples thereof include compounds in which 1 to 6 methylol groups are acyloxymethylated.

Examples of the guanamine compound include, for example, tetramethylolguanamine, tetramethoxymethylguanamine, tetramethoxymethylbenzoguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, tetramethoxyethylguanamine, tetraacyloxyguanamine, Examples thereof include compounds in which 1 to 4 methylol groups of tetramethylol guanamine are acyloxymethylated.

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

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. Can be mentioned.

Examples of the resol resin include phenol, alkylphenols such as cresol and xylenol, phenylphenol, resorcinol, biphenyl, bisphenols such as bisphenol A and bisphenol F, naphthol, phenolic hydroxyl group-containing compounds such as dihydroxynaphthalene, and aldehyde compounds. Examples thereof include polymers obtained by reacting under alkaline catalyst conditions.

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

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

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

Examples of the compound having a double bond such as the alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether and tetramethylene glycol divinyl ether. Vinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetra Examples thereof include vinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether and the like.

Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and 4 ,4'-(Isopropylidene)diphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, and other aromatic acid anhydrides; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydroanhydride Examples thereof include alicyclic carboxylic acid anhydrides such as phthalic acid, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, and trialkyltetrahydrophthalic anhydride.

Among the above-mentioned curing agents, glycoluril compounds, urea compounds and resole resins are preferable, and glycoluril compounds are more preferable, because high curability and a cured product having excellent heat resistance are obtained.

The curing agents may be used alone or in combination of two or more.
The content of the curing agent in the curable composition of the present invention is preferably 0.5 to 50 parts by mass based on 100 parts by mass of the total resin components of the curable composition of the present invention.

The curable composition of the present invention may contain the phenolic hydroxyl group-containing resin of the present invention and a curing agent, and may optionally contain other components.
Examples of the other components include resins other than the phenolic hydroxyl group-containing resin of the present invention, curing accelerators, surfactants, dyes, fillers, crosslinking agents, dissolution accelerators, and the like.

The curable composition of the present invention may contain a resin other than the resin containing a phenolic hydroxyl group of the present invention.
Examples of the other resins include novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, modified novolac resins of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, and phenol. Examples thereof include aralkyl resin (Zyloc resin), naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, biphenyl modified phenol resin, biphenyl modified naphthol resin, aminotriazine modified phenol resin and vinyl polymer.

Specific examples of the novolac resin include alkylphenols such as phenol, cresol and xylenol, phenylphenol, resorcinol, biphenyl, bisphenols such as bisphenol A and bisphenol F, naphthols, phenolic hydroxyl group-containing compounds such as dihydroxynaphthalene, and aldehyde compounds. Polymers and the like obtained by reacting ##STR1## under acid catalyst conditions are mentioned.

Specific examples of the vinyl polymer, polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, Examples thereof include homopolymers of vinyl compounds such as poly(meth)acrylate, and copolymers thereof.

The other resins may be used alone or in combination of two or more.
The content of the other resin in the curable composition of the present invention is not particularly limited and may be arbitrarily set depending on the desired application. For example, the amount of the other resin is preferably 0.5 to 100 parts by mass relative to 100 parts by mass of the phenolic hydroxyl group-containing resin of the present invention contained in the curable composition of the present invention.

The curable composition of the present invention may contain a curing accelerator.
Specific examples of the curing accelerator include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, manganese acetate, and the above-mentioned photoacid generator.

The curing accelerator may be used alone or in combination of two or more.
The content of the curing accelerator in the curable composition of the present invention is not particularly limited, and is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin solid content of the curable composition of the present invention. ..

The curable composition of the present invention is preferably prepared by dissolving the phenolic hydroxyl group-containing resin of the present invention in an organic solvent.
Examples of the organic solvent include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether propylene glycol monomethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diether. Dialkylene glycol dialkyl ethers such as propyl ether and diethylene glycol dibutyl ether; alkylene glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; acetone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone, etc. Ketone compound; cyclic ether such as dioxane; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2-hydroxy-3- Examples thereof include ester compounds such as methyl methyl butanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate and ethyl acetoacetate.

The organic solvent may be used alone or in combination of two or more.
The content of the organic solvent in the curable composition of the present invention is not particularly limited, and may be set, for example, to an amount that can dissolve all the phenolic hydroxyl group-containing resin of the present invention in the curable composition.

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

The curable composition of the present invention can be used as a resist material, and the cured product of the curable composition of the present invention can be used as a resist.
When the curable composition of the present invention is used as a resist material, the curable composition of the present invention may be used as it is as a coating material, or obtained by applying the curable composition of the present invention onto a support film. The coating film may be desolvated to obtain a resist film.
Examples of the support film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. The support film may be a single layer film or a laminated film composed of a plurality of films. The surface of the support film may be corona-treated or coated with a release agent.

When the curable composition of the present invention is used for a resist underlayer film, an example of a method for forming a resist underlayer film is as follows.
The curable composition of the present invention is applied onto an object to be subjected to photolithography such as a silicon substrate, a silicon carbide substrate, a gallium nitride substrate, and dried under a temperature condition of 100 to 200° C., and then at 250 to 400° C. The resist underlayer film is formed by a method such as heat curing under temperature conditions. Then, a normal photolithography operation is performed on this lower layer film to form a resist pattern, and a dry etching process with a halogen-based plasma gas or the like is performed to form a resist pattern by a multilayer resist method.

The method for curing the curable composition of the present invention is not particularly limited, and it can be cured by an appropriate method such as heat curing or photocuring depending on the type of curing agent, the type of curing accelerator and the like. The curing conditions such as the heating temperature and time in heat curing, the type of light rays in photocuring, and the exposure time are appropriately adjusted according to the type of curing agent, the type of curing accelerator, and the like.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
The number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the resins prepared in the examples are measured under the following GPC measurement conditions.
[GPC measurement conditions]
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation
Column: Showa Denko KK "Shodex KF802" (8.0 mm Φ×300 mm) + Showa Denko KK "SHODX KF802" (8.0 mm Φ300 mm) + Showa Denko KK "Shodex KF803" (8.0 mm Φ×) 300 mm) + Showa Denko KK "Shodex KF804" (8.0 mm Φ 300 mm)
Column temperature: 40°C
Detector: RI (differential refractometer)
Data processing: "GPC-8020 model II version 4.30" manufactured by Tosoh Corporation
Developing solvent: Tetrahydrofuran flow rate: 1.0 mL/min Sample: 0.5% by mass of tetrahydrofuran solution in terms of resin solid content filtered by a microfilter Injection amount: 0.1 mL
Standard sample: Monodisperse polystyrene below (Standard sample: Monodisperse polystyrene)
Tosoh Corporation "A-500"
Tosoh Corporation "A-2500"
Tosoh Corporation “A-5000”
Tosoh Corporation "F-1"
Tosoh Corporation "F-2"
Tosoh Corporation "F-4"
Tosoh Corporation “F-10”
Tosoh Corporation “F-20”

In addition, the ¹³ C-NMR spectrum measurement in the examples was carried out using “AL-400” manufactured by JEOL Ltd., and the DMSO-d ₆ solution of the sample was analyzed for structural analysis. The measurement conditions of ¹³ C-NMR spectrum are shown below.
[ ¹³ C-NMR spectrum measurement conditions]
Measurement mode: SGNNE (1H complete decoupling method for NOE elimination)
Pulse angle: 45°C Pulse sample concentration: 30 wt%
Total number of times: 10,000 times

Synthetic Example 1 Synthesis of Phenolic Trinuclear Compound Containing Carboxylic Acid A 2000 ml four-necked flask equipped with a cooling tube was charged with 293.2 g (2.4 mol) of 2,5-xylenol and 150 g (1 mol) of 4-formylbenzoic acid. It was dissolved in 500 ml of acetic acid. After adding 5 ml of sulfuric acid while cooling in an ice bath, the mixture was heated with a mantle heater at 100° C. for 2 hours and stirred for reaction. After the reaction was completed, the obtained solution was reprecipitated with water to obtain a crude product. The crude product was redissolved in acetone and reprecipitated with water, and the obtained product was filtered and dried in vacuum to obtain 283 g of a pale pink crystal precursor compound (A-1). ..

As a result of ¹³ C-NMR spectrum measurement of the obtained precursor compound (A-1), it was confirmed to be a compound represented by the following structural formula. The GPC purity calculated from the GPC chart was 97.9%. A GPC chart and a ¹³ C-NMR chart of the precursor compound (A-1) are shown in FIG. 1 and FIG. 2, respectively.

Production Example 1 Synthesis of carboxylic acid-containing novolak type phenol resin In a 1000 ml four-necked flask equipped with a cooling tube, 188 g of the precursor compound (A-1) and 16 g of 92% paraformaldehyde (B-1) were charged, and then 500 ml of acetic acid was added. Dissolved in. After 10 ml of sulfuric acid was added while cooling in an ice bath, the mixture was heated to 80° C. in an oil bath and reacted with stirring for 4 hours. After completion of the reaction, water was added to the obtained solution to reprecipitate a crude product. The crude product was redissolved in acetone and further reprecipitated with water, and the precipitate was filtered off and vacuum dried to obtain 182 g of an orange powder novolac type phenol resin (C-1).
The obtained novolac type phenol resin (C-1) had a number average molecular weight (Mn) of 3946, a weight average molecular weight (Mw) of 8504, and a polydispersity (Mw/Mn) of 2.16.
The GPC chart and the ¹³ C-NMR chart of the obtained novolac type phenol resin (C-1) are shown in FIG. 3 and FIG. 4, respectively.

Example 1 Preparation of esterified novolac type phenolic resin (Z-1) 20 g of the carboxylic acid-containing novolac type phenolic resin (C-1) obtained in Production Example 1 and 2-in a 300 ml four-necked flask equipped with a cooling tube. After adding 100 ml of ethoxyethanol and adding 1 ml of sulfuric acid while cooling in an ice bath, stirring was continued at room temperature for 4 hours for reaction. After completion of the reaction, sulfuric acid was inactivated with 10 ml of triethylamine, water was added to the obtained solution to reprecipitate a crude product. The crude product was redissolved in acetone and further reprecipitated with water, and then the precipitate was filtered off and dried in vacuo to give 21.3 g of a novolac-type esterified phenolic resin (Z-1) as a light orange powder. Got

The obtained esterified novolac type phenol resin (Z-1) had a number average molecular weight (Mn) of 3183, a weight average molecular weight (Mw) of 5180, and a polydispersity (Mw/Mn) of 1.62. The esterification rate of the obtained esterified novolak phenolic resin (Z-1) was 52% as calculated from ¹³ C-NMR.
A GPC chart of the esterified novolac type phenol resin (Z-1) is shown in FIG. The ¹³ C-NMR chart of the esterified novolac type phenol resin (Z-1) is shown in FIG.

The esterification rate was calculated from the ratio of the integrated value of carbonyl carbon derived from a carboxyl group observed at 167 to 175 ppm and the integrated value of carbonyl carbon derived from an ester group observed at 155 to 164 ppm.

Example 2 Synthesis of esterified novolac type phenolic resin (Z-2) The reaction was carried out in the same manner as in Example 1 except that 100 ml of 2-propanol was used instead of 100 ml of 2-ethoxyethanol to obtain a light orange powder. 18.3 g of esterified novolac type phenol resin (Z-2) was obtained.

The obtained novolak esterified phenolic resin (Z-2) had a number average molecular weight (Mn) of 1772, a weight average molecular weight (Mw) of 2554, and a polydispersity (Mw/Mn) of 1.44. The esterification rate of the obtained esterified novolac type phenol resin (Z-2) calculated from ¹³ C-NMR was 35%.
A GPC chart of the esterified novolac type phenol resin (Z-2) is shown in FIG. The ¹³ C-NMR chart of the esterified novolac type phenol resin (Z-2) is shown in FIG.

Example 3 Synthesis of esterified novolac type phenol resin (Z-3) The reaction was carried out in the same manner as in Example 1 except that 100 ml of 2-methyl-2-propanol was used instead of 100 ml of 2-ethoxyethanol, and 19.2 g of esterified novolak type phenolic resin (Z-3) was obtained as an orange powder.

The number average molecular weight (Mn) of the obtained esterified novolak phenolic resin (Z-3) was 1074, the weight average molecular weight (Mw) was 1466, and the polydispersity (Mw/Mn) was 1.36. The esterification rate of the obtained esterified novolak type phenol resin (Z-3) calculated from ¹³ C-NMR was 15%.
A GPC chart of the esterified novolac type phenol resin (Z-3) is shown in FIG. The ¹³ C-NMR chart of the esterified novolac type phenol resin (Z-3) is shown in FIG.

Comparative Example 1 Synthesis of Novolac Resin (C′-2) In a 2 L four-necked flask equipped with a stirrer and a thermometer, 552 g (4 mol) of 2-hydroxybenzoic acid and 498 g of 1,4-bis(methoxymethyl)benzene were added. (3 mol), 2.5 g of p-toluenesulfonic acid and 500 g of toluene were charged, the temperature was raised to 120° C., and the methanol removal reaction was performed. The temperature was elevated and distilled under reduced pressure, and the residue was distilled off under reduced pressure at 230° C. for 6 hours to obtain 882 g of a pale yellow solid novolac resin (C′-2).
The number average molecular weight (Mn) of the novolac resin (C′-2) was 1016, the weight average molecular weight (Mw) was 2782, and the polydispersity (Mw/Mn) was 2.74. A GPC chart of the novolac resin (C'-2) is shown in FIG.

Comparative Example 2 Synthesis of Novolac Resin (C′-3) In a 2 L four-necked flask equipped with a stirrer and a thermometer, 648 g (6 mol) of m-cresol, 432 g (4 mol) of p-cresol and 2.5 g of oxalic acid ( 0.2 mol) and 42% formaldehyde (492 g) were charged, and the temperature was raised to 100° C. to react. It was dehydrated to 200° C. under normal pressure, distilled, and distilled under reduced pressure at 230° C. for 6 hours to obtain 736 g of a pale yellow solid novolac type phenol resin (C′-3).
The novolak resin (C′-3) had a number average molecular weight (Mn) of 1450, a weight average molecular weight (Mw) of 10316, and a polydispersity (Mw/Mn) of 7.116. A GPC chart of the novolac resin (C′-3) is shown in FIG.

Example 4 Preparation of Photosensitive Composition 20 parts by mass of the esterified novolac type phenolic resin (Z-1) prepared in Example 1 was dissolved in 75 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), and a photoacid was added to this solution. 5 parts by mass of the generator was added and dissolved. The resulting solution was microfiltered with a 0.1 μm polytetrafluoroethylene disc filter to prepare a photosensitive composition. The photo-acid generator was Sanwa Chemical Co., Ltd. “TME-triazine”. (2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine) was used.

The following evaluation was performed using the obtained photosensitive composition. The results are shown in Table 1.
(1) Evaluation of alkali developability The obtained photosensitive composition was applied onto a 5-inch silicon wafer by a spin coater so as to have a thickness of about 1 μm, and dried on a hot plate at 110° C. for 60 seconds to obtain silicon. A resin film was formed on the wafer. This operation was repeated to prepare a plurality of evaluation wafers.
The evaluation wafer was immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and after the immersion, it was dried on a hot plate at 110° C. for 60 seconds. The film thickness before and after the immersion in the developing solution was measured, and the value obtained by dividing the difference by 60 was taken as the alkali developability (ADR1 (Å/s)).
Two evaluation wafers were prepared, and one of them was used as a “non-exposure sample”. The other sample was exposed to a 200 mJ/cm ² ghi ray using a ghi ray lamp (“Multilight” manufactured by Ushio Inc.) as a “exposed sample”, and then heat treatment was performed at 110° C. for 120 seconds. .. Both the "non-exposed sample" and the "exposed sample" were immersed in an alkali developing solution (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and then dried on a hot plate at 110°C for 60 seconds. The film thickness of each sample before and after the immersion in the developing solution was measured, and the value obtained by dividing the difference by 60 was taken as the alkali developability [ADR2 (Å/s)].
The evaluation wafer was immersed in an alkaline developer (15% sodium carbonate aqueous solution) for 60 seconds, and after the immersion, dried on a hot plate at 110° C. for 60 seconds. The film thickness before and after the immersion in the developing solution was measured, and the value obtained by dividing the difference by 60 was taken as the alkali developability (ADR3 (Å/s)).
Two evaluation wafers were prepared, and one of them was used as a “non-exposure sample”. The other sample was exposed to a 200 mJ/cm ² ghi ray using a ghi ray lamp (“Multilight” manufactured by Ushio Inc.) as a “exposed sample”, and then heat treatment was performed at 110° C. for 120 seconds. .. Both the “non-exposed sample” and the “exposed sample” were immersed in an alkaline developer (15% sodium carbonate aqueous solution) for 60 seconds, and then dried on a 110° C. hot plate for 60 seconds. The film thickness of each sample before and after the immersion in the developing solution was measured, and the value obtained by dividing the difference by 60 was taken as the alkali developability [ADR4 (Å/s)].

(2) Evaluation of heat resistance The obtained photosensitive composition was applied onto a 5-inch silicon wafer by a spin coater so as to have a thickness of about 1 μm, and dried on a hot plate at 110° C. for 60 seconds. The resin film on the wafer was scraped off, and its glass transition temperature (Tg) was measured and evaluated.
The glass transition temperature (Tg) was measured by using a differential scanning calorimeter (DSC) (“Q100” manufactured by TA Instruments Co., Ltd.) under a nitrogen atmosphere in a temperature range of −100 to 200° C. and a temperature rising temperature of 10° C./ It went under the condition of minute. When the obtained glass transition temperature was 150° C. or higher, it was evaluated as “◯”, and when it was less than 150° C., it was evaluated as “x”.

Example 5-6 and Comparative Example 3-5
A photosensitive composition was prepared and evaluated in the same manner as in Example 4 except that the resin shown in Table 1 was used instead of the esterified novolac type phenol resin (Z-1). The results are shown in Table 1.

As the results in Table 1 show, it was found that the photosensitive compositions of Comparative Examples 3-5 could not function as a photosensitive composition because alkali elution was observed before the exposure. On the other hand, in the photosensitive compositions of Examples 4 to 6, alkali elution was not observed in the stage before exposure, and it was found that alkali elution was caused by exposure and good development contrast was obtained. It is speculated that this is because the acid of the photo-acid generator hydrolyzes the ester group of the esterified novolak-type phenol resin of Example 1-3 to form a carboxyl group, thereby changing the polarity.

Claims

Phenol, which is a reaction product of a novolac-type phenol resin (C) and an alcohol compound (X), in which an aromatic compound (A) represented by the following formula (1) and an aliphatic aldehyde (B) are essential reaction raw materials. Resin containing water-soluble hydroxyl group.

(In the formula (1), R 1 and R 2 each independently represent an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group or a halogen atom.
m, n and p each independently represent an integer of 0-4.
When R 1 is a plurality, the plurality of R 1 may be the same or different.
When R 2 are a plurality, the plurality of R 2 may be the same or different.
R 3 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural moiety having at least one substituent selected from an alkoxy group, a halogen group and a hydroxyl group on the hydrocarbon group.
R 4 represents a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group or a halogen atom.
If R 4 is plural, R 4 may be the same or different. )
The phenol according to claim 1, wherein the aromatic compound (A) is a reaction product of an alkyl-substituted phenol compound and one or more selected from an aromatic aldehyde having a carboxyl group and an aromatic ketone having a carboxyl group. Resin containing water-soluble hydroxyl group.
The phenolic hydroxyl group-containing resin according to claim 2, wherein the aromatic aldehyde having a carboxyl group is formylbenzoic acid.
The phenolic hydroxyl group-containing resin according to any one of claims 1 to 3, wherein the aliphatic aldehyde (B) is one or more selected from formaldehyde and paraformaldehyde.
The phenolic hydroxyl group-containing resin according to any one of claims 1 to 4, wherein the alcohol compound (X) is one or more selected from aliphatic alcohols having 10 or less carbon atoms and ether alcohols having 10 or less carbon atoms. ..
The phenolic hydroxyl group-containing resin according to any one of claims 1 to 5, wherein the novolac type phenolic resin (C) has a carboxyl group esterification rate of 5 to 70 mol%.
A photosensitive composition comprising the phenolic hydroxyl group-containing resin according to any one of claims 1 to 6 and a photoacid generator.
A resist film comprising the photosensitive composition according to claim 7.
A curable composition comprising the phenolic hydroxyl group-containing resin according to any one of claims 1 to 6 and a curing agent.
A cured product of the curable composition according to claim 9.
A resist film comprising the curable composition according to claim 9.