KR102652307B1 - Phenolic hydroxyl group-containing resin, photosensitive composition, resist film, curable composition and cured product - Google Patents

Abstract

With the goal of providing a phenolic hydroxyl group-containing resin that has high heat resistance and exhibits excellent alkali developability when used as a resist material, an aromatic compound (A) and an aliphatic aldehyde (B) represented by the following formula (1) are prepared. Provided is a phenolic hydroxyl group-containing resin that is a reaction product of a novolak-type phenol resin (C), which is used as an essential reaction raw material, and an alcohol compound (X). In formula (1), R ₁ and R ₂ are 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 are integers from 0 to 4. R ₃ is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural moiety having one or more substituents selected from an alkoxy group, a halogen group, and a hydroxyl group on a hydrocarbon group. R ₄ is a hydroxyl group, an aliphatic hydrocarbon group having 1 to 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, methods for forming a wide variety of resist patterns, subdivided according to use and function, are being developed one after another, and along with this, the performance requirements for resist resin materials are becoming more advanced and more diverse. For example, as a resist used in the manufacture of semiconductors such as IC and LSI, the manufacture of display devices such as LCD, and the manufacture of printing plates, etc., photosensitive agents such as alkali-soluble resins and 1,2-naphthoquinonediazide compounds are used. Positive type photoresists are known.

As the alkali-soluble resin, a positive photoresist composition using a cresol novolak-type epoxy resin has been proposed (for example, see Patent Documents 1 and 2).

Positive photoresist compositions using cresol novolak-type epoxy resins were developed for the purpose of improving sensitivity and other developability, but in recent years, as semiconductors have become more highly integrated, there is a tendency for patterns to become thinner. Better sensitivity is required. However, a positive photoresist composition using a cresol novolak-type epoxy resin had the problem of not being able to obtain sufficient sensitivity corresponding to line thinning. In addition, since various heat treatments are performed in the manufacturing process of semiconductors and the like, higher heat resistance is also required, but positive photoresist compositions using cresol novolak-type epoxy resins have a problem of not having sufficient heat resistance.

As a fabrication of patterned structures using photoresists, there is wafer level packaging technology. Wafer level packaging technology is a packaging technology that manufactures a semiconductor package by performing resin encapsulation, rewiring, and electrode formation in the wafer state, and dividing it into pieces by dicing.

In wafer level packaging, as wiring density increases, electrochemical deposition methods are being used for electronic wiring (for example, see Non-Patent Document 1). The gold bumps, copper posts and copper wires used for repositioning wafer level packaging require a mold of resist to be electroplated. This resist layer is very thick compared to the resist layer used in IC manufacturing. The size of the resist pattern and the thickness of the resist layer are both, 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).

For patterning of a high aspect ratio photoresist, it has been proposed to use an aliphatic polyaldehyde as a coagulant for metacresol or para-cresol when synthesizing a novolak resin (see, for example, Patent Document 3). However, there was a problem in that it was difficult to achieve both heat resistance and alkali dissolution speed, which are important characteristics as a thick film resist.

Japanese Patent Publication No. 2008-0881197 Japanese Patent Publication No. 2002-107925 Japanese Patent Publication No. 9-6003

Gary Solomon, Electrochemically deposited solder bumps for wafer-level packaging, PACKAGING/ASSEMBLY, Solid State Technology, pages 83, 84, 86, 88 April 2001

The problem that the present invention seeks to solve is to provide a phenolic hydroxyl group-containing resin that has high heat resistance and exhibits excellent alkali developability when used as a resist material.

The present inventors have conducted intensive studies to solve the above problems and have found that a phenolic hydroxyl group-containing resin is a reaction product of a triaryl compound containing a carboxyl group and an aliphatic aldehyde, in which some or all of the carboxyl groups in the reactant are esterified with an alcohol compound. discovered that it was excellent in heat resistance and alkali developability, and completed the present invention.

That is, the present invention is a reaction product of a novolak-type phenol resin (C) and an alcohol compound ( It relates to a phenolic hydroxyl group-containing resin.

(In the above 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 to 4.

When there is a plurality of R ₁ , the plurality of R ₁ may be the same or different from each other.

When there is a plurality of R ₂ , the plurality of R ₂ may be the same or different from each other.

R ₃ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural moiety having one or more substituents selected from an alkoxy group, a halogen group, and a hydroxyl group on a 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 there is a plurality of R ₄ , the plurality of R ₄ may be the same or different from each other)

According to the present invention, it is possible to provide a phenolic hydroxyl group-containing resin that has high heat resistance and exhibits excellent alkali developability when used as a resist material.

Figure 1 shows a GPC chart of a carboxylic acid-containing phenolic ternary compound (A-1).
Figure 2 is a diagram showing a ¹³ C-NMR chart of the carboxylic acid-containing phenolic ternary compound (A-1).
Figure 3 is a diagram showing a GPC chart of novolak-type phenolic resin (C-1).
Figure 4 is a diagram showing a ¹³ C-NMR chart of novolak-type phenolic resin (C-1).
Figure 5 is a diagram showing a GPC chart of esterified novolak-type phenolic resin (Z-1).
Figure 6 is a diagram showing a ¹³ C-NMR chart of esterified novolak-type phenolic resin (Z-1).
Figure 7 is a diagram showing a GPC chart of esterified novolak-type phenolic resin (Z-2).
Figure 8 is a diagram showing a ¹³ C-NMR chart of esterified novolak-type phenol resin (Z-2).
Figure 9 is a diagram showing a GPC chart of esterified novolak-type phenolic resin (Z-3).
Figure 10 is a diagram showing a ¹³ C-NMR chart of esterified novolak-type phenolic resin (Z-3).
Figure 11 is a diagram showing a GPC chart of novolac resin (C'-2).
Figure 12 is a diagram showing a GPC chart of novolak resin (C'-3).

Hereinafter, one embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and can be implemented with appropriate changes without impairing the effect of the present invention.

[Phenolic hydroxyl group-containing resin]

The phenolic hydroxyl group-containing resin of the present invention is a novolak-type phenol resin (C) and an alcohol compound (X) containing an aromatic compound (A) and an aliphatic aldehyde (B) represented by the following formula (1) as essential reaction raw materials. It is a reactant of

(In the above 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 to 4.

When there is a plurality of R ₁ , the plurality of R ₁ may be the same or different from each other.

When there is a plurality of R ₂ , the plurality of R ₂ may be the same or different from each other.

R ₃ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural moiety having one or more substituents selected from an alkoxy group, a halogen group, and a hydroxyl group on a 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 there is a plurality of R ₄ , the plurality of R ₄ may be the same or different from each other)

The phenolic hydroxyl group-containing resin of the present invention has a triarylmethane structure. Since it contains aromatic rings at high density by having the triarylmethane structure, the phenolic hydroxyl group-containing resin of the present invention has very high heat resistance.

In the triarylmethane structure of the formula (1), the two hydroxy groups and the carboxyl group are substituted with different aromatic rings, and a strong hydrogen bond is not formed. As a result, the phenol hydroxyl group-containing resin of the present invention can maintain good proton dissociation properties and exhibit excellent alkali developability. In addition, some or all of the carboxyl groups in the triarylmethane structure are esterified by reaction with the alcohol compound (X), resulting in extreme polarity changes before and after hydrolysis of the ester group (before and after formation of the carboxyl group) , good developing contrast can be obtained.

[Novolak-type phenol resin]

The novolak-type phenol resin (C) is a resin containing an aromatic compound (A) represented by the following formula (1) and an aliphatic aldehyde (B) as essential reaction raw materials.

(In the above 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 to 4.

When there is a plurality of R ₁ , the plurality of R ₁ may be the same or different from each other.

When there is a plurality of R ₂ , the plurality of R ₂ may be the same or different from each other.

R ₃ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural moiety having one or more substituents selected from an alkoxy group, a halogen group, and a hydroxyl group on a 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 there is a plurality of R ₄ , the plurality of R ₄ may be the same or different from each other)

In the formula (1), the aliphatic hydrocarbon group having 1 to 9 carbon atoms for R ₁ , R ₂ , R ₃ and R ₄ is methyl, ethyl, propyl, isopropyl, butyl, and t-butyl. , alkyl groups with 1 to 9 carbon atoms, such as hexyl group, cyclohexyl group, heptyl group, octyl group, and nonyl group, and cycloalkyl groups with 3 to 9 carbon atoms.

In the above formula (1), examples of the alkoxy groups of R ₁ , R ₂ and R ₄ include methoxy group, ethoxy group, propyloxy group, butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, etc. there is.

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

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

In the above formula (1), examples of the halogen atoms of 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), the “structural moiety having one or more substituents selected from an alkoxy group, a halogen group, and a hydroxyl group on the hydrocarbon group” of R ₃ includes a halogenated alkyl group, a halogenated aryl group, and 2-methoxyethoxy group. , alkoxyalkoxy groups such as 2-ethoxyethoxy group, and alkylalkoxy groups substituted with hydroxy groups.

In the above formula (1), m and n are each preferably an integer of 2 or 3.

When m and n are each 2, it is preferable that two R ₁ and two R ₂ are each independently an alkyl group having 1 to 3 carbon atoms. At this time, it is preferable that two R ₁ and two R ₂ are each bonded to the 2,5-position of the phenolic hydroxyl group.

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

The aromatic compound (A) represented by the above formula (1) may be used individually as one having the same structure, or may be used as a plurality of compounds having different molecular structures.

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 between an alkyl-substituted phenol (a1) and an aromatic ketone (a3) having a carboxyl group.

Alkyl-substituted phenol (a1) is a phenol in which an alkyl group has been substituted. Examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms, and a methyl group is preferable.

Specific examples of alkyl substituted phenol (a1) include o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, p-octylphenol, p-t-butylphenol, o-cyclo monoalkyl phenol such as hexyl phenol, m-cyclohexyl phenol, and p-cyclohexyl phenol; dialkylphenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,4-xylenol, and 2,6-xylenol; Trialkyl phenols such as 2,3,5-trimethyl phenol and 2,3,6-trimethyl phenol, etc. can be mentioned. Among these, dialkylphenol is preferable, and 2,5-xylenol and 2,6-xylenol are more preferable.

Alkyl-substituted phenol (a1) may be used individually or in combination of two or more types.

Examples of the aromatic aldehyde (a2) having a carboxyl group include compounds having a formyl group on the benzene ring, such as benzene, phenol, and resorcinol, and compounds having an alkyl group, an alkoxy group, a halogen atom, etc. in addition to the formyl group.

Specific examples of aromatic aldehyde (a2) having a carboxyl group include 4-formylbenzoic acid, 2-formylbenzoic acid, 3-formylbenzoic acid, methyl 4-formylbenzoate, ethyl 4-formylbenzoate, and propyl 4-formylbenzoate. , 4-formylbenzoate isopropyl, 4-formylbenzoate butyl, 4-formylbenzoate isobutyl, 4-formylbenzoate tertiary butyl, 4-formylbenzoate cyclohexyl, 4-formylbenzoate terrioctyl, etc. can be mentioned. Among these, 4-formylbenzoic acid is preferable.

The aromatic aldehyde (a2) having a carboxyl group may be used individually or in combination of two or more types.

Aromatic ketone (a3) having a carboxyl group is a compound having at least one carboxyl group and a 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, ethyl 2-acetylbenzoate, and propyl 2-acetylbenzoate. Examples include isopropyl 2-acetylbenzoate, butyl 2-acetylbenzoate, isobutyl 2-acetylbenzoate, tert-butyl 2-acetylbenzoate, cyclohexyl 2-acetylbenzoate, and tert-octyl 2-acetylbenzoate. Among these, 2-acetylbenzoic acid and 4-acetylbenzoic acid are preferred.

Aromatic ketone (a3) may be used individually or in combination of two or more types.

Specific examples of aliphatic aldehyde (B) include formaldehyde, paraformaldehyde, 1,3,5-trioxane, acetaldehyde, propionaldehyde, tetraoxymethylene, polyoxymethylene, chloral, hexamethylenetetramine, glyoxal, Examples include n-butyraldehyde, caproaldehyde, allylaldehyde, crotonaldehyde, and acrolein.

The aliphatic aldehyde compound (B) may be used individually or in combination of two or more types.

The aliphatic aldehyde (B) is preferably at least one selected from formaldehyde and paraformaldehyde, and formaldehyde is more preferable.

When using formaldehyde and an aliphatic aldehyde other than formaldehyde as the aliphatic aldehyde (B), the amount of the aliphatic aldehyde other than formaldehyde used is preferably in the range of 0.05 to 1 mole per mole of formaldehyde.

The method for producing the novolak-type phenol resin (C) preferably includes the following three processes 1 to 3.

(Process 1)

An aromatic compound (A) is obtained by polycondensing an alkyl-substituted phenol (a1) and an aromatic aldehyde (a2) having a carboxyl group by heating at a temperature of 60 to 140° C. in the presence of an acid catalyst, using a solvent as necessary. .

(Process 2)

The aromatic compound (A) obtained in Step 1 is isolated from the reaction solution.

(Process 3)

The aromatic compound (A) and the aliphatic aldehyde (B) isolated in step 2 are heated and polycondensed in the range of 60 to 140°C in the presence of an acid catalyst, using a solvent as necessary, to produce a novolak-type phenol resin ( C) is obtained.

Examples of the acid catalyst used in steps 1 and 3 include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts may be used alone or in combination of two or more types. Moreover, 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 because of their excellent activity. Additionally, the acid catalyst may be added before or during the reaction.

Examples of solvents used as necessary in steps 1 and 3 include 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 , polyols such as 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, and glycerin; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethylmethyl ether, ethylene glycol mono Glycol ethers such as phenyl ether; Cyclic ethers such as 1,3-dioxane and 1,4-dioxane; Glycol esters such as ethylene glycol acetate; Ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Aromatic hydrocarbons such as toluene and xylene can be mentioned. These solvents may be used alone or in combination of two or more types. Moreover, among these solvents, 2-ethoxyethanol is preferable because it has excellent solubility of the obtained compound.

The input ratio of alkyl-substituted phenol (a1) and aromatic aldehyde (a2) having a carboxyl group [(a1)/(a2)] in step 1 is determined by the removal of unreacted alkyl-substituted phenol (a1) and the yield of the product. And because the purity of the reaction product is excellent, 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.

The charging ratio [(A)/(B)] of the aromatic compound (A) and the aliphatic aldehyde (B) in step 3 is capable of suppressing excessive high molecular weight (gelation) and is appropriate as a phenolic resin for resist. Since a molecular weight product can be obtained, 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.

As a method of isolating the aromatic compound (A) from the reaction solution in step 2, for example, the reaction solution is put into a poor solvent (S1) in which the reaction product is insoluble or sparingly soluble, the obtained precipitate is separated by filtration, and then the reaction is carried out. One method is to dissolve the product in a solvent (S2) that is also miscible with the poor solvent (S1), add it back to the poor solvent (S1), and filter the resulting precipitate.

Examples of the poor solvent (S1) used at this time include water; monoalcohols such as methanol, ethanol, and propanol; Aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, and cyclohexane; Aromatic hydrocarbons such as toluene and xylene can be mentioned. 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, 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 , polyols such as 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, and glycerin; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethylmethyl ether, ethylene glycol mono Glycol ethers such as phenyl ether; Cyclic ethers such as 1,3-dioxane and 1,4-dioxane; Glycol esters such as ethylene glycol acetate; Ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone can be mentioned. In addition, when water is used as the poor solvent (S1), acetone is preferable as the (S2). In addition, the poor solvent (S1) and solvent (S2) may be used alone or in combination of two or more types.

When an aromatic hydrocarbon such as toluene or xylene is used as a solvent in Steps 1 and 3, when heated above 80°C, the aromatic compound (A) produced by the reaction dissolves in the solvent, so by cooling as is. Since crystals of the aromatic compound (A) precipitate, the aromatic compound (A) can be isolated by filtering and separating the crystals. In this case, it is not necessary to use the poor solvent (S1) and solvent (S2).

By the isolation method in Step 2 described above, the aromatic compound (A) represented by the above formula (1) can be obtained.

The purity of the aromatic compound (A) is preferably 90% or more, more preferably 94% or more, and especially preferably 98% or more as calculated from a gel permeation chromatography (GPC) chart. The purity of the aromatic compound (A) can be determined from the area ratio of the GPC chart, and is measured under the measurement conditions described later.

The weight average molecular weight (Mw) of the novolak-type phenol resin (C) is preferably in the range of 2,000 to 35,000, and more preferably in the range of 2,000 to 25,000.

The weight average molecular weight (Mw) of the novolak-type phenol resin (C) was measured under the following measurement conditions using gel permeation chromatography (hereinafter abbreviated as "GPC").

(GPC measurement conditions)

Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation.

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

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

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

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

Column temperature: 40℃

Detector: RI (differential refractometer)

Data processing: Tosoh Corporation “GPC-8020 Model II Version 4.30”

Development solvent: tetrahydrofuran

Flow rate: 1.0 ml/min

Sample: 0.5% by mass of tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100㎕)

Standard sample: monodisperse polystyrene below

(Standard sample: monodisperse polystyrene)

“A-500” made by Tosoh Corporation

“A-2500” manufactured by Tosoh Corporation.

“A-5000” manufactured by Tosoh Corporation.

“F-1” made by Tosoh Corporation

“F-2” made by Tosoh Corporation

“F-4” made by Tosoh Corporation

“F-10” made by Tosoh Corporation

“F-20” made by Tosoh Corporation

[Alcohol compound (X)]

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

The alcohol compound (X) includes carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, propylene glycol, and trimethylolpropane. 10 or less aliphatic alcohols; 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, 3-methoxy-1-butyl alcohol, 2-isopropoxyethyl Ether alcohols containing ether bonds such as alcohols and having 10 or less carbon atoms; Keto alcohols with 10 or less carbon atoms containing a ketone group such as 3-hydroxy-2-butanone; and ester alcohols having 10 or less carbon atoms containing an ester group such as methyl hydroxyisobutyrate. Among these, aliphatic alcohols with 10 or less carbon atoms and ether alcohols with 10 or less carbon atoms are preferred, and ethyl alcohol, n-propyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, and isobutyl alcohol ( More preferred are 2-methyl-2-propanol), t-butyl alcohol and 2-ethoxyethyl alcohol (2-ethoxyethanol).

The alcohol compound (X) may be used individually or in combination of two or more types.

The dehydration esterification reaction can be performed by stirring a mixture of the novolak-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, p-toluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts may be used individually or in combination of two or more types.

The reaction temperature is not particularly limited, but may be in the range of, for example, 10°C to 60°C, and room temperature is preferable since no special equipment is required.

The dehydration esterification reaction of the novolak-type phenol resin (C) and the alcohol compound (X) is a reaction between the carboxyl group in the novolak-type phenol resin (C) derived from the aromatic compound (A) represented by the above formula (1) and the alcohol compound. (X) reacts, and an ester bond is formed with dehydration.

In the dehydration esterification reaction, the input ratio of the novolak-type phenol resin (C) and the alcohol compound (X) is not particularly limited, but is, for example, phenol resin/alcohol = 1/0.5 to 1/10 in weight ratio. .

The phenolic hydroxyl group-containing resin of the present invention is a resin containing a structure in which part or all of the carboxyl groups of the novolak-type phenol resin (C) are esterified, and the esterification rate of the carboxyl groups of the novolak-type phenol resin (C) is: Preferably it is 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 the 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, and 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, and more preferably in the range of 5,000 to 15,000.

The number average molecular weight and weight average molecular weight of the phenolic hydroxyl group-containing resin of the present invention are the same as those of the novolak-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 photoacid generator is not particularly limited, and known photoacid generators can be used, and examples include organic halogen compounds, sulfonic acid esters, onium salts, diazonium salts, and disulfone compounds.

Specific examples of the photoacid generator include the following.

Tris(trichloromethyl)-s-triazine, tris(tribromomethyl)-s-triazine, tris(dibromomethyl)-s-triazine, 2,4-bis(tribromomethyl)- 6-p-methoxyphenyl-s-triazine, (2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine), etc. haloalkyl group-containing s-triazine derivatives;

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

benzene derivatives containing a haloalkyl group such as bis(trichloromethyl)benzene and bis(tribromomethyl)benzene; Sulfone compounds containing haloalkyl groups such as tribromomethylphenylsulfone and trichloromethylphenylsulfone; Halogen-containing sulfolane compounds such as 2,3-dibromosulfolane; isocyanurate compounds containing a haloalkyl group such as tris(2,3-dibromopropyl)isocyanurate;

Triphenylsulfonium chloride, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, Sulfonium salts such as triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroarsenate, and triphenylsulfonium hexafluorophosphonate;

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

Methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, phenyl p-toluenesulfonate, 1,2,3-tris(p-toluenesulfonyloxy)benzene, p-toluenesulfonate Benzoin ester, methyl methanesulfonate, ethyl methanesulfonate, butyl methanesulfonate, 1,2,3-tris(methanesulfonyloxy)benzene, phenyl methanesulfonate, benzoin methanesulfonate, trifluoromethane. Methyl sulfonate, ethyl trifluoromethanesulfonate, butyl trifluoromethanesulfonate, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, phenyl trifluoromethanesulfonate, trifluoromethane Sulfonic acid ester compounds such as sulfonic acid benzoin ester; 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-methoxy Phenylsulfonyl)diazomethane, cyclopentylsulfonyl-(3-methoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(4-methoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-( 2-Fluorophenylsulfonyl)diazomethane, cyclohexylsulfonyl-(3-fluorophenylsulfonyl)diazomethane, cyclohexylsulfonyl-(4-fluorophenylsulfonyl)diazomethane, cyclophene Tylsulfonyl-(2-fluorophenylsulfonyl)diazomethane, cyclopentylsulfonyl-(3-fluorophenylsulfonyl)diazomethane, cyclopentylsulfonyl-(4-fluorophenylsulfonyl)diazo Methane, cyclohexylsulfonyl-(2-chlorophenylsulfonyl)diazomethane, cyclohexylsulfonyl-(3-chlorophenylsulfonyl)diazomethane, cyclohexylsulfonyl-(4-chlorophenylsulfonyl)diazomethane Zomethane, 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-trifluoromethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(3-trifluoromethylphenylsulfonyl)diazomethane Pentylsulfonyl-(4-trifluoromethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2-trifluoromethoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(3-trifluoromethoxy) Phenylsulfonyl)diazomethane, cyclohexylsulfonyl-(4-trifluoromethoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2-trifluoromethoxyphenylsulfonyl)diazomethane, cyclophene Tylsulfonyl-(3-trifluoromethoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(4-trifluoromethoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2,4,6- Trimethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2,3,4-trimethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2,4,6-triethylphenylsulfonyl)diazo Methane, 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 Zomethane, phenylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane, phenylsulfonyl-(2,3,4-trimethylphenylsulfonyl)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)diazomethane, phenylsulfonyl-(2-fluorophenylsulfonyl)diazo Sulfone diazide compounds such as methane, phenylsulfonyl-(3-fluorophenylsulfonyl)diazomethane, and phenylsulfonyl-(4-fluorophenylsulfonyl)diazomethane;

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

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

Sulfonium salts that are salts of sulfonium cations such as triaryl sulfonium and trialalkyl sulfonium and sulfonates such as fluoroalkane sulfonate, arenesulfonate, and alkane sulfonate;

iodonium salts that are salts of iodonium cations such as diaryliodonium and sulfonates such as fluoroalkane sulfonate, arenesulfonate, and alkanesulfonate;

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

N-sulfonyloxyimide compounds consisting of a combination of dicarboxylic acid imide compounds and sulfonates such as fluoroalkane sulfonate, arenesulfonate, and alkane sulfonate;

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

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

Nitrobenzylsulfonate compounds such as (poly)nitrobenzyl fluoroalkanesulfonic acid, (poly)nitrobenzyl arenesulfonic acid, and (poly)nitrobenzyl alkanesulfonic acid;

Fluoroalkanebenzylsulfonate compounds such as (poly)fluoroalkanebenzyl fluoroalkanesulfonic acid, (poly)fluoroalkanebenzyl arenesulfonic acid, and (poly)fluoroalkanebenzyl alkanesulfonic acid;

Bis(arylsulfonyl)alkane compounds;

Bis-O-(arylsulfonyl)-α-dialkylglyoxime, bis-O-(arylsulfonyl)-α-dicycloalkylglyoxime, bis-O-(arylsulfonyl)-α-diarylgly Oxime, bis-O-(alkylsulfonyl)-α-dialkylglyoxime, bis-O-(alkylsulfonyl)-α-dicycloalkylglyoxime, bis-O-(alkylsulfonyl)-α-dia Lilglyoxime, bis-O-(fluoroalkylsulfonyl)-α-dialkylglyoxime, bis-O-(fluoroalkylsulfonyl)-α-dicycloalkylglyoxime, bis-O-(fluoro Alkylsulfonyl)-α-diarylglyoxime, bis-O-(arylsulfonyl)-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-dialkylnioxime, bis-O-(fluoroalkylsulfonyl)-α-dicycloalkyl oxime compounds such as nioxime and bis-O-(fluoroalkylsulfonyl)-α-diarylnioxime;

Arylsulfonyloxyiminoarylacetonitrile, Alkylsulfonyloxyiminoarylacetonitrile, Fluoroalkylsulfonyloxyiminoarylacetonitrile, ((arylsulfonyl)oxyimino-thiophene-ylidene)arylacetonitrile , ((alkylsulfonyl)oxyimino-thiophene-ylidene)arylacetonitrile, ((fluoroalkylsulfonyl)oxyimino-thiophene-ylidene)arylacetonitrile, bis(arylsulfonyloxyimino)aryl Lendiacetonitrile, bis(alkylsulfonyloxyimino)arylenediacetonitrile, bis(fluoroalkylsulfonyloxyimino)arylenediacetonitrile, arylfluoroalkanone-O-(alkylsulfonyl)oxime, Modified oxime compounds such as arylfluoroalkanone-O-(arylsulfonyl)oxime and arylfluoroalkanone-O-(fluoroalkylsulfonyl)oxime.

The photoacid generator may be used individually, or two or more types may be used in combination.

The content of the photoacid generator in the photosensitive composition of the present invention is, for example, in the range of 0.1 to 20 parts by mass, preferably in the range of 0.1 to 10 parts by mass, based on 100 parts by mass of the resin solid content in the photosensitive composition.

When the content of the photoacid generator is within the above range, the photosensitive composition of the present invention can be made into a photosensitive composition with high photosensitivity.

The photosensitive composition of the present invention may contain the phenolic hydroxyl group-containing resin of the present invention and the above-mentioned photoacid 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, photosensitive agents, 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, the effect of preventing dimensional changes in the resist pattern due to migration of acid generated from the photoacid generator is obtained.

Specific examples of the above organic base compounds include pyrimidine, (poly)aminopyrimidine, (poly)hydroxypyrimidine, (poly)amino(poly)hydroxypyrimidine, (poly)amino(poly)alkylpyrimidine, ( Pyrimidine compounds such as poly)amino(poly)alkoxypyrimidine, (poly)hydroxy(poly)alkylpyrimidine, and (poly)hydroxy(poly)alkoxypyrimidine; Pyridine compounds such as pyridine, (poly)alkylpyridine, and dialkylaminopyridine; amine compounds containing hydroxyalkyl groups such as polyalkanolamine, tri(hydroxyalkyl)aminoalkane, and bis(hydroxyalkyl)iminotris(hydroxyalkyl)alkane; Aminoaryl compounds such as aminophenol, etc. can be mentioned.

The said organic base compound may be used individually by 1 type, or may use 2 or more types together.

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 more preferably in the range of 1 to 50 mol%, based on 1 mole of the photoacid generator.

The photosensitive composition of the present invention may contain other resins other than the phenolic hydroxyl group-containing resin of the present invention.

The other resins mentioned above are not particularly limited, and are, for example, resins that are soluble in alkaline developing solutions, or resins that are soluble in alkaline developing solutions when used in combination with additives such as photoacid generators.

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

Specific examples of phenol resins other than the phenolic hydroxyl group-containing resin of the present invention include phenol novolak resin, cresol novolak resin, naphthol novolak resin, coaxial novolak resin using various phenolic compounds, aromatic hydrocarbon formaldehyde resin-modified phenol Resin, dicyclopentadienephenol addition type resin, phenol aralkyl resin (xyloxy resin), naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, biphenyl modified phenol resin (polyhydric where the phenol nucleus is linked to a bismethylene group) phenolic compounds), biphenyl-modified naphthol resin (polyhydric naphthol compound whose phenol core is linked to a bismethylene group), aminotriazine-modified phenol resin (polyhydric phenol compound whose phenol core is linked to melamine, benzoguanamine, etc.), or aromatic ring containing an alkoxy group. and phenolic resins such as modified novolac resins (polyhydric phenol compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).

Among the specific examples of phenolic resins other than the phenolic hydroxyl group-containing resin of the present invention, cresol novolak resin and co-axiality of cresol with other phenolic compounds are used in that they provide a photosensitive composition with an excellent balance of developability, heat resistance, and fluidity. Novolak resin is preferred.

Cresol novolak resin or coaxial novolak resin with cresol and another phenolic compound specifically uses one or more cresols selected from o-cresol, m-cresol, and p-cresol and an aldehyde compound as essential reaction raw materials. , It is a novolak resin obtained by using a combination of other phenolic compounds.

The other resins mentioned above may be used individually or in combination of two or more types.

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

The photosensitive composition of the present invention may contain a photosensitive agent commonly used as a resist material. The photosensitizer is, for example, a compound having a quinonediazide group.

Specific examples of the compound having the quinonediazide group include ester compounds or amidates of an aromatic (poly)hydroxy compound and a sulfonic acid compound having a quinonediazide group. In addition, the ester compound is meant to include partial ester compounds, and the amidate is meant to include partial amides.

Specific examples of the sulfonic acid compounds having the quinonediazide group include naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, and orthoanthraquinonediazide. Sulfonic acid, 1,2-naphthoquinone-2-diazide-5-sulfonic acid, etc. can be mentioned.

As a specific example of the sulfonic acid compound having the quinonediazide group, a halide further substituted by halogen can also be used.

Examples of the aromatic (poly)hydroxy compound include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, and 2,4,6-trihydroxybenzophenone. , 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2', 4,4'-Tetrahydroxybenzophenone, 2,3',4,4',6-pentahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, 2,2 ',3,4,5-pentahydroxybenzophenone, 2,3',4,4',5',6-hexahydroxybenzophenone, 2,3,3',4,4',5'- polyhydroxybenzophenone compounds such as hexahydroxybenzophenone;

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

Tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydride Roxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis( Tris such as 4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, etc. (hydroxyphenyl)methane compound or its methyl substituent;

Bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4 -Hydroxyphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2 -methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-3 -Hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-3-hydride Roxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl Bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methane compounds such as -2-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane or methyl substituents thereof can be mentioned.

The said photosensitizer may be used individually by 1 type, or may use 2 or more types together.

The content of the photosensitive agent in the photosensitive composition of the present invention is preferably 5 to 50 parts by mass with respect to a total of 100 parts by mass of the resin component of the photosensitive composition of the present invention, since it results in a photosensitive composition with excellent photosensitivity.

The photosensitive composition of the present invention may contain a surfactant. When the photosensitive composition of the present invention contains a surfactant, effects such as improved film forming properties and pattern adhesion and reduction of development defects are obtained when the photosensitive composition of the present invention is used for resist applications.

The surfactant may be a known surfactant. Examples of the surfactant include nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants.

The said surfactant may be used individually by 1 type, or may use 2 or more types together.

The content of the surfactant in the photosensitive composition of the present invention is preferably 0.001 to 2 parts by mass with respect to a total of 100 parts by mass of the resin component 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 and propylene glycol monomethyl ether; dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; Alkylene glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate; Ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; Cyclic ethers such as dioxane; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2-hydroxy-3-methylbutanoate, 3-methoxy Ester compounds such as butylacetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate can be mentioned.

The said organic solvent may be used individually by 1 type, or may use 2 or more types together.

The content of the organic solvent in the photosensitive composition of the present invention is not particularly limited. For example, it may be set to an amount that can dissolve all of 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 mixing the above components and mixing them using a stirrer or the like. Additionally, when the photosensitive composition of the present invention contains fillers or pigments, it can be produced by dispersing or mixing using a dispersing device such as a resolver, homogenizer, or three roll mill.

The photosensitive composition of the present invention can be used as a resist material.

When using the photosensitive composition of the present invention as a resist material, the photosensitive composition of the present invention may be used as is as a ceramic material, or the photosensitive composition of the present invention may be applied on a support film, and the obtained coating film may be desolvated to form a resist film. You can do this.

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 made of multiple films. Additionally, the surface of the support film may be corona treated or coated with a release agent.

General photolithography methods using the photosensitive composition of the present invention include, for example, the following methods.

First, the photosensitive composition of the present invention is applied on an object to be photolithographed, such as a silicon substrate, silicon carbide substrate, or gallium nitride substrate, and prebaked at a temperature of 60 to 150°C. The application 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, a resist pattern is formed by exposure through a resist pattern and development with an alkaline developer.

When using the photosensitive composition of the present invention for a permanent resist film, it may include a crosslinking agent.

Examples of the crosslinking agent include those similar to the curing agent contained in the curable composition described later.

The said crosslinking agent may be used individually by 1 type, or may use 2 or more types together.

Methods for forming the resist permanent film include, for example, the following methods.

First, the photosensitive composition of the present invention is applied on an object to be photolithographed, such as a silicon substrate, silicon carbide substrate, or gallium nitride substrate, and prebaked at a temperature of 60 to 150°C. The application method is the same as above. Next, a resist pattern is formed by exposure through a resist pattern, further heat-curing under temperature conditions of 110 to 210°C, and then developing with an alkaline developer. Alternatively, after exposure, it may first be developed with an alkaline developer and then heat-cured under temperature conditions of 110 to 210°C.

Specific examples of the permanent resist film include solder resist, packaging materials, underfill materials, package adhesive layers for circuit elements, adhesive layers between integrated circuit elements and circuit boards, etc. in semiconductor devices. Additionally, in thin displays such as LCD and OLED, thin film transistor protective films, liquid crystal color filter protective films, black matrices, spacers, etc. can be used.

[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 that can cause a curing reaction with the phenolic hydroxyl group-containing resin of the present invention. For example, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, resol resins, epoxy compounds, Isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, acid anhydrides, oxazoline compounds, etc. are included.

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

Examples of the guanamine compounds include tetramethylolguanamine, tetramethoxymethylguanamine, tetramethoxymethylbenzoguanamine, compounds in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, Examples include compounds in which 1 to 4 methylol groups of tetramethoxyethyl guanamine, tetraacyloxyguanamine, and tetramethylol guanamine are acyloxymethylated.

Examples of the glycoluril compounds include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3, 4,6-tetrakis(hydroxymethyl)glycoluril, etc. can be mentioned.

Examples of the urea compounds include 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methyl)urea. Toximethyl)urea, etc. can be mentioned.

Examples of the resol resin include phenol, alkylphenol such as cresol and xylenol, phenylphenol, resorcinol, biphenyl, bisphenol such as bisphenol A and bisphenol F, and phenolic such as naphthol and dihydroxynaphthalene. and a polymer obtained by reacting a hydroxyl group-containing compound and an aldehyde compound under alkaline catalyst conditions.

Examples of the epoxy compound include diglycidyloxynaphthalene, phenol novolak-type epoxy resin, cresol novolak-type epoxy resin, naphthol novolak-type epoxy resin, naphthol-phenol coaxial novolak-type epoxy resin, and naphthol-cresol. Coaxial 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, trimethylene ether type epoxy resin Examples include phenylmethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phosphorus atom-containing epoxy resin, and polyglycidyl ether of a cocondensate of a phenolic hydroxyl group-containing compound and an alkoxy group-containing aromatic compound. .

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

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

Examples of compounds containing double bonds such as the alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, and 1,4-butanediol divinyl. Ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl Ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, etc.

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

Among the above curing agents, glycoluril compounds, urea compounds, and resol resins are preferable, and glycoluril compounds are more preferable because high curability is obtained and a cured product with excellent heat resistance is obtained.

The said hardening|curing agent may be used individually by 1 type, or may use 2 or more types together.

The content of the curing agent in the curable composition of the present invention is preferably 0.5 to 50 parts by mass with respect to a total of 100 parts by mass of the 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 and the curing agent of the present invention, and may optionally contain other components.

Examples of the other components include other resins other than the phenolic hydroxyl group-containing resin of the present invention, curing accelerators, surfactants, dyes, fillers, crosslinking agents, and dissolution accelerators.

The curable composition of the present invention may contain other resins other than the phenolic hydroxyl group-containing resin 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, and modified novolak resins of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds. , phenol aralkyl resin (xyloxy resin), naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, aminotriazine-modified phenol resin, vinyl polymer, etc. I can hear it.

Specific examples of the novolak resin include alkylphenols such as phenol, cresol, and xylenol, phenylphenol, resorcinol, biphenyl, bisphenol such as bisphenol A and bisphenol F, and phenolic hydroxyl groups such as naphthol and dihydroxynaphthalene. and a polymer obtained by reacting a containing compound with an aldehyde compound under acid catalyst conditions.

Specific examples of the vinyl polymer include polyhydroxystyrene, polystyrene, polyvinyl naphthalene, polyvinyl anthracene, polyvinyl carbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, and polytetracyclododecene. , homopolymers of vinyl compounds such as polynortricyclene and poly(meth)acrylate, or copolymers thereof.

The other resins mentioned above may be used individually or in combination of two or more types.

The content of the other resins in the curable composition of the present invention is not particularly limited and may be set arbitrarily according to the desired use. For example, it is preferable that the amount of the other resins is 0.5 to 100 parts by mass based on 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, p-toluenesulfonic acid, zinc acetate, manganese acetate, and the above-mentioned photoacid generators.

The said hardening accelerator may be used individually by 1 type, or 2 or more types may be used together.

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 and propylene glycol monomethyl ether; dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; Alkylene glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate; Ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; Cyclic ethers such as dioxane; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2-hydroxy-3-methylbutanoate, 3-methoxy Ester compounds such as butylacetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate can be mentioned.

The said organic solvent may be used individually by 1 type, or may use 2 or more types together.

The content of the organic solvent in the curable composition of the present invention is not particularly limited. For example, it may be set to an amount that can dissolve all of 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 mixing the above components and mixing them using a stirrer or the like. Additionally, when the curable composition of the present invention contains fillers or pigments, it can be produced by dispersing or mixing using a dispersing device such as a dissolver, homogenizer, or 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 using the curable composition of the present invention as a resist material, the curable composition of the present invention may be used as is as a coating material, or the curable composition of the present invention may be applied on a support film, and the obtained coating film may be desolvated to form a resist. You can also do it with 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 made of multiple films. Additionally, the surface of the support film may be corona treated or coated with a release agent.

When using the curable composition of the present invention for a resist underlayer film, the following is an example of a method for creating a resist underlayer film.

The curable composition of the present invention is applied on an object to be photolithographed, such as a silicon substrate, silicon carbide substrate, or gallium nitride substrate, dried under a temperature condition of 100 to 200 ° C., and then further heated under a temperature condition of 250 to 400 ° C. A resist underlayer film is formed by a method such as curing. Next, a normal photolithographic operation is performed on this underlayer film to form a resist pattern, and dry etching is performed with a halogen-based plasma gas or the like to form a resist pattern by the multilayer resist method.

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

[Example]

Hereinafter, the present invention will be described in detail through examples and comparative examples.

In addition, the number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity (Mw/Mn) of the resin prepared in the examples were measured under the following GPC measurement conditions.

[GPC measurement conditions]

Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation.

Column: “Shodex KF802” (8.0mmФ×300mm) manufactured by Showa Denko Corporation + “Shodex KF802” (8.0mmФ×300mm) manufactured by Showa Denko Corporation + “Shodex KF803” manufactured by Showa Denko Corporation ( 8.0mmФ×300mm) + Showa Denko Co., Ltd. “Shodex KF804” (8.0mmФ×300mm)

Column temperature: 40℃

Detector: RI (differential refractometer)

Data processing: Tosoh Corporation “GPC-8020 Model II Version 4.30”

Development solvent: tetrahydrofuran

Flow rate: 1.0 mL/min

Sample: 0.5 mass% tetrahydrofuran solution in terms of resin solid content filtered through a micro filter.

Injection volume: 0.1ml

Standard sample: monodisperse polystyrene below

(Standard sample: monodisperse polystyrene)

“A-500” made by Tosoh Corporation

“A-2500” manufactured by Tosoh Corporation.

“A-5000” manufactured by Tosoh Corporation.

“F-1” made by Tosoh Corporation

“F-2” made by Tosoh Corporation

“F-4” made by Tosoh Corporation

“F-10” made by Tosoh Corporation

“F-20” made by Tosoh Corporation

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

[ ¹³ C-NMR spectrum measurement conditions]

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

Pulse angle: 45℃ pulse

Sample concentration: 30wt%

Integration count: 10000 times

Synthesis Example 1 Synthesis of carboxylic acid-containing phenolic ternary compound

293.2 g (2.4 mol) of 2,5-xylenol and 150 g (1 mol) of 4-formylbenzoic acid were added to a 2000 ml four-necked flask equipped with a cooling tube and dissolved in 500 ml of acetic acid. After adding 5 ml of sulfuric acid while cooling in an ice bath, it was heated and stirred at 100°C for 2 hours using a mantle heater to cause reaction. After completion of the reaction, the obtained solution was subjected to reprecipitation with water to obtain a crude product. The crude product was re-dissolved in acetone and further reprecipitated with water, and then the obtained product was filtered and dried under vacuum to obtain 283 g of precursor compound (A-1) as pale colored crystals.

As a result of measuring the ¹³ C-NMR spectrum of the obtained precursor compound (A-1), it was confirmed that it was a compound represented by the following structural formula. Additionally, the GPC purity calculated from the GPC chart was 97.9%. The GPC chart of the precursor compound (A-1) is shown in FIG. 1, and ^{the 13} C-NMR chart is shown in FIG. 2.

Preparation Example 1 Synthesis of carboxylic acid-containing novolak-type phenol resin

188 g of precursor compound (A-1) and 16 g of 92% paraformaldehyde (B-1) were added to a 1000 ml four-necked flask equipped with a cooling tube, and then dissolved in 500 ml of acetic acid. After adding 10 ml of sulfuric acid while cooling in an ice bath, it was heated to 80°C in an oil bath and allowed to react while stirring for 4 hours. After completion of the reaction, water was added to the obtained solution to reprecipitate the crude product. The crude product was re-dissolved in acetone and further reprecipitated with water, and then the precipitate was separated by filtration and dried under vacuum to obtain 182 g of novolak-type phenol resin (C-1) as an orange powder.

The number average molecular weight (Mn) of the obtained novolak-type phenol resin (C-1) was 3946, the weight average molecular weight (Mw) was 8504, and the polydispersity (Mw/Mn) was 2.16.

The GPC chart of the obtained novolak-type phenol resin (C-1) is shown in FIG. 3, and ^{the 13} C-NMR chart is shown in FIG. 4.

Example 1 Preparation of esterified novolak-type phenolic resin (Z-1)

20 g of the carboxylic acid-containing novolak-type phenol resin (C-1) obtained in Preparation Example 1 and 100 ml of 2-ethoxyethanol were added to a 300 ml four-necked flask equipped with a cooling tube, and 1 ml of sulfuric acid was added while cooling in an ice bath. After addition, stirring was continued for 4 hours at room temperature to allow reaction. After completion of the reaction, sulfuric acid was deactivated with 10 ml of triethylamine, and water was added to the resulting solution to reprecipitate the crude product. The crude product was redissolved in acetone and further reprecipitated with water, and then the precipitate was separated by filtration and dried under vacuum to obtain 21.3 g of novolak-type esterified phenol resin (Z-1) as a light orange powder.

The obtained esterified novolak-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. Additionally, the esterification rate calculated from ¹³ C-NMR of the obtained esterified novolak-type phenol resin (Z-1) was 52%.

The GPC chart of the esterified novolak-type phenolic resin (Z-1) is shown in Figure 5. The ¹³ C-NMR chart of the esterified novolak-type phenol resin (Z-1) is shown in Figure 6.

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

Example 2 Synthesis of esterified novolak-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, and 18.3 g of esterified novolak-type phenol resin (Z-2) as a light orange powder was obtained.

The number average molecular weight (Mn) of the obtained novolak-type esterified phenol resin (Z-2) was 1772, the weight average molecular weight (Mw) was 2554, and the polydispersity (Mw/Mn) was 1.44. Additionally, the esterification rate calculated from ¹³ C-NMR of the obtained esterified novolak-type phenol resin (Z-2) was 35%.

The GPC chart of the esterified novolak-type phenol resin (Z-2) is shown in Figure 7. The ¹³ C-NMR chart of the esterified novolak-type phenol resin (Z-2) is shown in Figure 8.

Example 3 Synthesis of esterified novolak-type phenolic 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 phenol resin (Z-3) as a pale orange powder was obtained. got it

The obtained esterified novolak-type phenol resin (Z-3) had a number average molecular weight (Mn) of 1074, a weight average molecular weight (Mw) of 1466, and a polydispersity (Mw/Mn) of 1.36. Additionally, the esterification rate calculated from ¹³ C-NMR of the obtained esterified novolak-type phenol resin (Z-3) was 15%.

The GPC chart of the esterified novolak-type phenolic resin (Z-3) is shown in Figure 9. The ¹³ C-NMR chart of the esterified novolak-type phenol resin (Z-3) is shown in Figure 10.

Comparative Example 1 Synthesis of novolak resin (C'-2)

In a 2L four-necked flask equipped with a stirrer and thermometer, add 552 g (4 mol) of 2-hydroxybenzoic acid, 498 g (3 mol) of 1,4-bis(methoxymethyl)benzene, 2.5 g of p-toluenesulfonic acid, and 500 g of toluene. It was added, the temperature was raised to 120°C, and demethanol reaction was performed. The temperature was raised under reduced pressure, distilled, and distilled under reduced pressure at 230°C for 6 hours to obtain 882 g of light yellow solid novolak 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. The GPC chart of novolac resin (C'-2) is shown in Figure 11.

Comparative Example 2 Synthesis of novolac resin (C'-3)

Add 648 g (6 mol) of m-cresol, 432 g (4 mol) of p-cresol, 2.5 g (0.2 mol) of oxalic acid, and 492 g of 42% formaldehyde to a 2L four-necked flask equipped with a stirrer and thermometer, and raise the temperature to 100°C. , reacted. Dehydration and distillation were performed at normal pressure to 200°C, and distillation under reduced pressure was performed at 230°C for 6 hours to obtain 736 g of light yellow solid novolak-type phenol resin (C'-3).

The number average molecular weight (Mn) of the novolac resin (C'-3) was 1450, the weight average molecular weight (Mw) was 10316, and the polydispersity (Mw/Mn) was 7.116. The GPC chart of novolak resin (C'-3) is shown in Figure 12.

Example 4 Preparation of photosensitive composition

20 parts by mass of the esterified novolak-type phenol resin (Z-1) prepared in Example 1 was dissolved in 75 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), and 5 parts by mass of a photoacid generator was added to this solution and dissolved. The obtained solution was microfiltered through a 0.1 μm polytetrafluoroethylene disk filter to prepare a photosensitive composition.

In addition, the photoacid generator is "TME-triazine" (2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl) manufactured by Sanwa Chemical Co., Ltd. -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 to 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 to form a resin film on the silicon wafer. This operation was repeated to prepare multiple wafers for evaluation.

The wafer for evaluation was immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and dried on a hot plate at 110°C for 60 seconds after immersion. The film thickness before and after immersion in the developing solution was measured, and the difference divided by 60 was taken as alkaline developability (ADR1 (Å/s)).

Two wafers for evaluation were prepared, and one was used as a “sample without exposure.” The other side was used as an “exposed sample” and was irradiated with 200 mJ/cm 2 of ghi rays using a ghi ray lamp (“Multi Light” manufactured by Ushio Denki Co., Ltd.), followed by heat treatment at 110°C for 120 seconds. Both the “sample without exposure” and the “sample with exposure” were immersed in an alkaline developer (2.38% aqueous tetramethylammonium hydroxide solution) for 60 seconds, and then dried on a hot plate at 110°C for 60 seconds. The film thickness of each sample was measured before and after immersion in the developing solution, and the difference divided by 60 was taken as alkaline developability [ADR2 (Å/s)].

The wafer for evaluation was immersed in an alkaline developer (15% aqueous sodium carbonate solution) for 60 seconds, and dried on a hot plate at 110°C for 60 seconds after immersion. The film thickness before and after immersion in the developing solution was measured, and the difference divided by 60 was taken as alkaline developability (ADR3 (Å/s)).

Two wafers for evaluation were prepared, and one was used as a “sample without exposure.” The other side was used as an “exposed sample” and was irradiated with 200 mJ/cm 2 of ghi rays using a ghi ray lamp (“Multi Light” manufactured by Ushio Denki Co., Ltd.), followed by heat treatment at 110°C for 120 seconds. Both the “sample without exposure” and the “sample with exposure” were immersed in an alkaline developer (15% aqueous sodium carbonate solution) for 60 seconds, and then dried on a hot plate at 110°C for 60 seconds. The film thickness of each sample was measured before and after immersion in the developing solution, and the difference divided by 60 was taken as alkaline developability [ADR4 (Å/s)].

(2) Evaluation of heat resistance

The obtained photosensitive composition was applied to a 5-inch silicon wafer with a spin coater to a thickness of about 1 μm, and dried on a hot plate at 110°C for 60 seconds. The resin film on the wafer was scraped off, and its glass transition temperature (Tg) was measured and evaluated.

The measurement of the glass transition temperature (Tg) was performed using a differential scanning calorimeter (DSC) (“Q100” manufactured by TA Instruments Co., Ltd.) under the conditions of a temperature range of -100 to 200°C and a temperature increase temperature of 10°C/min under a nitrogen atmosphere. . The case where the obtained glass transition temperature was 150°C or higher was evaluated as “○”, and the case where it was less than 150°C was evaluated as “×”.

Examples 5 to 6 and Comparative Examples 3 to 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 novolak-type phenol resin (Z-1). The results are shown in Table 1.

[Table 1]

As the results in Table 1 show, alkali elution was confirmed in the photosensitive compositions of Comparative Examples 3 to 5 in the stage before exposure, and it can be seen that they cannot function as photosensitive compositions. On the other hand, it can be seen that in the photosensitive compositions of Examples 4 to 6, alkali elution was not confirmed in the stage before exposure, but alkali elution occurred upon exposure, and good development contrast was obtained. This is presumed to be because the ester group of the esterified novolak-type phenol resin of Examples 1 to 3 was hydrolyzed by the acid of the photo acid generator to form a carboxyl group, thereby changing the polarity.

Claims (12)

It is a phenolic hydroxyl group-containing resin that is a reaction product between a novolak-type phenol resin (C) and an alcohol compound (X).
The novolak-type phenol resin (C) is a phenolic hydroxyl group-containing resin that uses an aromatic compound (A) and an aliphatic aldehyde (B) represented by the following formula (1) as essential reaction raw materials.

(In the above 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 to 4.
When there is a plurality of R ₁ , the plurality of R ₁ may be the same or different from each other.
When there is a plurality of R ₂ , the plurality of R ₂ may be the same or different from each other.
R ₃ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural moiety having one or more substituents selected from an alkoxy group, a halogen group, and a hydroxyl group on a 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 there is a plurality of R ₄ , the plurality of R ₄ may be the same or different from each other) According to paragraph 1,
A phenolic hydroxyl group-containing resin in which the aromatic compound (A) is a reaction product of an alkyl-substituted phenol compound and at least one selected from aromatic aldehydes having a carboxyl group and aromatic ketones having a carboxyl group. According to paragraph 2,
A phenolic hydroxyl group-containing resin wherein the aromatic aldehyde having the carboxyl group is formylbenzoic acid. According to any one of claims 1 to 3,
A phenolic hydroxyl group-containing resin wherein the aliphatic aldehyde (B) is at least one selected from formaldehyde and paraformaldehyde. According to any one of claims 1 to 3,
A phenolic hydroxyl group-containing resin wherein the alcohol compound (X) is at least one selected from aliphatic alcohols having 10 or less carbon atoms and ether alcohols having 10 or less carbon atoms. According to any one of claims 1 to 3,
A phenolic hydroxyl group-containing resin in which the esterification rate of the carboxyl group of the novolak-type phenol resin (C) is 5 to 70 mol%. A photosensitive composition comprising the phenolic hydroxyl group-containing resin according to any one of claims 1 to 3 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 3 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. According to claim 1 or 2,
A phenolic hydroxyl group-containing resin wherein the alcohol compound (X) is an aliphatic alcohol with 10 or less carbon atoms, an ether alcohol with 10 or less carbon atoms, or both.

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