CN112346302A

CN112346302A - Positive photosensitive resin composition, method for forming patterned resist film, and patterned resist film

Info

Publication number: CN112346302A
Application number: CN202010770166.7A
Authority: CN
Inventors: 松本直纯
Original assignee: Tokyo Ohka Kogyo Co Ltd
Current assignee: Tokyo Ohka Kogyo Co Ltd
Priority date: 2019-08-06
Filing date: 2020-08-03
Publication date: 2021-02-09

Abstract

The present invention relates to a positive photosensitive resin composition, a method for forming a patterned resist film, and a patterned resist film. The invention provides a positive photosensitive resin composition which can form a patterned resist film with a good cross-sectional shape and has high sensitivity, a method for forming a patterned resist film using the positive photosensitive resin composition, and a patterned resist film formed by the positive photosensitive resin composition. The solution is that the positive photosensitive resin composition comprises: novolac resin (A); a quinonediazido group-containing compound (B); a sensitizer (C) which is a compound having a phenolic hydroxyl group and has a molecular weight of 1000 or less; and a phenolic hydroxyl group-containing resin (D) other than the Novolac resin (A) having a weight-average molecular weight of more than 1000 in an amount within a predetermined range.

Description

Positive photosensitive resin composition, method for forming patterned resist film, and patterned resist film

Technical Field

The present invention relates to a positive photosensitive resin composition, a method for forming a patterned resist film, and a patterned resist film.

Background

As a method for forming a wiring or a terminal on a substrate, a method is known in which a metal layer is etched using a resist pattern as a mask pattern, or plating is performed using a resist pattern as a mold pattern for plating.

As a method for forming a resist pattern when forming a wiring or a terminal on a substrate, the following method is generally used: a dry film formed of a negative photosensitive composition is used to form a photosensitive composition layer on a substrate, and the photosensitive composition layer is exposed and developed. However, when a negative photosensitive composition is used, there are the following problems: insufficient resolution; or sometimes it is difficult to peel the resist pattern from the substrate; and so on.

As a method for solving the above problem, there is a method for forming a resist pattern using a positive photosensitive composition which has good resolution and is relatively easy to be peeled from a substrate.

As a positive photosensitive composition that can be used for forming a wiring, a terminal, or the like made of a metal, for example, a photosensitive composition containing an alkali-soluble Novolac resin such as a cresol Novolac resin, a photosensitizer, and a benzotriazole-based compound is known (see patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese patent application laid-open No. 2010-176012

Disclosure of Invention

Problems to be solved by the invention

When forming fine wiring and terminals, it is desired to: a resist pattern having a cross-sectional shape close to a rectangular shape can be formed using the photosensitive composition; the photosensitive composition is highly sensitive. However, it is difficult to achieve both a good cross-sectional shape of the resist pattern and high sensitivity with the positive photosensitive composition described in patent document 1.

The present invention has been made in view of the above problems, and an object thereof is to provide a positive photosensitive resin composition which can form a patterned resist film having a good cross-sectional shape and has high sensitivity, a method for forming a patterned resist film using the positive photosensitive resin composition, and a patterned resist film formed from the positive photosensitive resin composition.

Means for solving the problems

The inventors of the present application have found that by including in a positive photosensitive resin composition: novolac resin (A); a quinonediazido group-containing compound (B); a sensitizer (C) which is a compound having a phenolic hydroxyl group and has a molecular weight of 1000 or less; and a phenolic hydroxyl group-containing resin (D) in an amount within a predetermined range, wherein the weight average molecular weight of the resin (D) is more than 1000 in addition to the Novolac resin (A), whereby the above-mentioned problems can be solved, and the present invention has been completed. Specifically, the present invention provides the following.

The first embodiment of the present invention is a positive photosensitive resin composition comprising a Novolac resin (A), a quinonediazido group-containing compound (B), a sensitizer (C), and a phenolic hydroxyl group-containing resin (D),

the sensitizer (C) is a compound having a phenolic hydroxyl group with a molecular weight of 1000 or less,

the phenolic hydroxyl group-containing resin (D) is a resin having a weight average molecular weight of more than 1000 other than the Novolac resin (A),

the content of the phenolic hydroxyl group-containing resin (D) is 0.5 to 10 parts by mass with respect to 100 parts by mass of the Novolac resin (a).

A second aspect of the present invention is a method for forming a patterned resist film, including the steps of:

a step of forming a coating film by coating the positive photosensitive resin composition according to the first aspect on a substrate;

a step of exposing the coating film in a position-selective manner; and the combination of (a) and (b),

and developing the exposed coating film with a developer.

A third aspect of the present invention is a patterned resist film formed from the positive photosensitive resin composition according to the first aspect.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a positive photosensitive resin composition capable of forming a patterned resist film having a good cross-sectional shape and having high sensitivity, a method for forming a patterned resist film using the positive photosensitive resin composition, and a patterned resist film formed from the positive photosensitive resin composition can be provided.

Detailed Description

Positive photosensitive resin composition

The positive photosensitive resin composition comprises a Novolac resin (A), a quinonediazido group-containing compound (B), a sensitizer (C), and a phenolic hydroxyl group-containing resin (D).

The sensitizer (C) is a compound having a phenolic hydroxyl group with a molecular weight of 1000 or less.

The phenolic hydroxyl group-containing resin (D) is a resin having a weight average molecular weight of more than 1000 other than the Novolac resin (a).

The content of the phenolic hydroxyl group-containing resin (D) is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the Novolac resin (a).

The positive photosensitive resin composition having the above-described structure can realize both a good cross-sectional shape and high sensitivity of a patterned resist film.

Hereinafter, essential or optional components contained in the positive photosensitive resin composition will be described.

< Novolac resin (A) >)

As the Novolac resin (a), various Novolac resins conventionally blended in positive photosensitive resin compositions can be used. The Novolac resin (a) is preferably obtained by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenol") with an aldehyde in the presence of an acid catalyst.

Phenols

Examples of the phenols include: phenol; cresols such as o-cresol, m-cresol and p-cresol; xylenols such as 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, and 3, 5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol; alkylphenols such as 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; trialkylphenols such as 2,3, 5-trimethylphenol and 3,4, 5-trimethylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone monomethyl ether, pyrogallol, and phloroglucinol; alkyl polyphenols such as alkylresorcinol, alkylcatechol, and alkylhydroquinone (all of alkyl groups have 1 to 4 carbon atoms); alpha-naphthol; beta-naphthol; hydroxybiphenyl; and bisphenol A and the like. These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferable, and m-cresol and p-cresol are more preferable in combination. In this case, various characteristics such as sensitivity as a positive photosensitive resin composition and heat resistance of a resist film to be formed can be adjusted by adjusting the blending ratio of the two. The mixing ratio of m-cresol and p-cresol is not particularly limited, and is preferably 3/7 or more and 8/2 or less in terms of a mass ratio of m-cresol/p-cresol. When the proportion of m-cresol is 3/7 or more, the sensitivity as a positive photosensitive resin composition can be improved. When the ratio of m-cresol is 8/2 or less, the heat resistance of a resist film formed using the photosensitive resin composition can be improved.

Aldehydes

Examples of the aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone, or two or more of them may be used in combination.

Acid catalyst

Examples of the acid catalyst include: inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfuric acid, and p-toluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

Molecular weight

The weight average molecular weight (Mw; hereinafter, also simply referred to as "weight average molecular weight") of the Novolac resin (a) in terms of polystyrene is preferably 1000 or more, more preferably 2000 or more, and even more preferably 3000 or more, from the viewpoint of developability, resolution, and the like of the positive photosensitive resin composition. The weight average molecular weight of the Novolac resin (a) is preferably 50000 or less, more preferably 40000 or less, still more preferably 30000 or less, and still more preferably 20000 or less.

The dispersion degree (weight average molecular weight Mw/number average molecular weight Mn) of the Novolac resin (a) is preferably 1 or more and 20 or less, more preferably 2 or more and 17 or less, particularly preferably 3 or more and 15 or less, and further preferably 4 or more and 12 or less.

In the present specification, the weight average molecular weight Mw and the number average molecular weight Mn may be defined as relative values in terms of polystyrene in GPC (gel permeation chromatography) measurement.

When a plurality of the Novolac resins (a) are used, GPC (gel permeation chromatography) measurement may be performed in a state where these plurality of the Novolac resins (a) are combined, and the degree of dispersion may be determined from the obtained spectrum.

As the Novolac resin (a), at least two resins having different weight average molecular weights in terms of polystyrene may be used in combination. By using resins having different weight average molecular weights in combination, various excellent characteristics such as developability, resolution, film-forming property, and the like can be imparted to the positive photosensitive resin composition.

The combination of the resins having different weight average molecular weights with respect to the Novolac resin (a) is not particularly limited. The combination is preferably a combination of a resin having a low weight average molecular weight of 1000 to 10000 inclusive and a resin having a high weight average molecular weight of 5000 to 50000 inclusive, more preferably a combination of a resin having a low weight average molecular weight of 2000 to 8000 inclusive and a resin having a high weight average molecular weight of 8000 to 40000 inclusive, and still more preferably a combination of a resin having a low weight average molecular weight of 3000 to 7000 inclusive and a resin having a high weight average molecular weight of 10000 to 20000 inclusive.

When resins having different weight average molecular weights are used in combination as the Novolac resin (a), the content of each is not particularly limited. The content of the resin on the low weight average molecular weight side in the total amount of the Novolac resin (a) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. On the other hand, the content of the resin on the low weight average molecular weight side in the total amount of the Novolac resin (a) is preferably 50% by mass or less, and more preferably 40% by mass or less.

The ratio of the mass of the Novolac resin (a) to the entire solid content of the positive photosensitive resin composition is not particularly limited as long as the positive photosensitive resin composition contains the desired amounts of the quinonediazido group-containing compound (B), the sensitizer (C), and the phenolic hydroxyl group-containing resin (D).

The ratio of the mass of the Novolac resin (a) to the total solid content of the positive photosensitive resin composition is preferably 40 mass% or more and 80 mass% or less, more preferably 45 mass% or more and 75 mass% or less, and still more preferably 50 mass% or more and 70 mass% or less.

< Compound (B) containing a quinonediazido group >

The positive photosensitive resin composition contains a quinonediazido group-containing compound (B). The quinonediazide group-containing compound (B) can be appropriately selected from compounds having quinonediazide groups which are blended in conventional various positive photosensitive resin compositions.

Preferable specific examples of the quinonediazide-group-containing compound (B) include a complete ester compound, a partial ester compound, an amide compound, a partial amide compound, and the like, of a quinonediazide-group-containing sulfonic acid, wherein: polyhydroxy benzophenones such as 2,3, 4-trihydroxybenzophenone, 2,4,4 ' -trihydroxybenzophenone, 2,4, 6-trihydroxybenzophenone, 2,3, 4-trihydroxy-2 ' -methylbenzophenone, 2,3,4,4 ' -tetrahydroxybenzophenone, 2 ', 4,4 ' -tetrahydroxybenzophenone, 2,3 ', 4,4 ', 6-pentahydroxybenzophenone, 2 ', 3,4,4 ' -pentahydroxybenzophenone, 2 ', 3,4, 5-pentahydroxybenzophenone, 2,3 ', 4,4 ', 5 ', 6-hexahydroxybenzophenone, 2,3,3 ', 4,4 ', 5 ' -hexahydroxybenzophenone, and 2,3,3 ', 4,4 ', 5 ' -hexahydroxybenzophenone; bis [ (poly) hydroxyphenyl ] ethylidene } bisphenols such as 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 '- {1- [4- [ 2- (4-hydroxyphenyl) -2-propyl ] phenyl ] ethylidene } bisphenol, and 3, 3' -dimethyl- {1- [4- [ 2- (3-methyl-4-hydroxyphenyl) -2-propyl ] phenyl ] ethylidene } bisphenol Alkanes; tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3, 5-dimethylphenyl) -4-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -4-hydroxyphenyl methane, bis (4-hydroxy-3, 5-dimethylphenyl) -2-hydroxyphenyl methane, tris (hydroxyphenyl) methanes such as bis (4-hydroxy-2, 5-dimethylphenyl) -2-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -3, 4-dihydroxyphenyl methane, and bis (4-hydroxy-3, 5-dimethylphenyl) -3, 4-dihydroxyphenyl methane, or methyl-substituted products thereof; bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenyl methane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenyl methane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenyl methane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenyl methane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenyl methane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenyl methane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenyl methane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenyl methane, bis (3-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenyl methane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenyl methane, bis (3-cyclohexyl-4-hydroxy-2-hydroxyphenyl) methane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -2-hydroxyphenylmethane, and bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane Bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes such as alkanes and methyl-substituted compounds thereof; hydroxyl or amino group-containing compounds such as phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, catechol, pyrogallol monomethyl ether, pyrogallol-1, 3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine, and 4, 4' -diaminobenzophenone; and pyrogallol-acetone resins and the like. These quinonediazide group-containing compounds (B) may be used alone or in combination of two or more.

The quinonediazide-containing sulfonic acid used as the quinonediazide-containing compound (B) is not particularly limited. Examples thereof include: naphthoquinone-1, 2-diazide-5-sulfonic acid, naphthoquinone-1, 2-diazide-4-sulfonic acid and other diazide naphthoquinone sulfonic acids; ortho-anthraquinone diazido sulfonic acid, and the like. Among these, diazidonaphthoquinone sulfonic acid is preferable. The above ester compound containing a quinonediazido sulfonic acid, preferably a naphthoquinonediazidosulfonic acid, is well dissolved in a solvent which is generally used when a positive composition is used in the form of a solution, and has good compatibility with the Novolac resin (a). When these compounds are blended as the quinonediazido group-containing compound (B) in the positive photosensitive resin composition, a highly sensitive positive photosensitive resin composition can be easily obtained.

The method for producing the above ester compound as the quinonediazido group-containing compound (B) is not particularly limited. For example, the following methods can be mentioned: the quinone diazide group-containing sulfonic acid is added in the form of a sulfonyl chloride such as naphthoquinone-1, 2-diazide-sulfonyl chloride, and condensed in a solvent such as dioxane in the presence of a base such as triethanolamine, a base of carbonic acid, or a base of carbonic acid hydrogen, thereby carrying out complete esterification or partial esterification.

From the viewpoint of good sensitivity and resolution of the positive photosensitive resin composition and the viewpoint of easy formation of a patterned resist film having a good shape using the positive photosensitive resin composition, it is also preferable that the positive photosensitive resin composition comprises, in combination, a compound represented by the following formula (B1), a compound represented by the following formula (B2), and a compound represented by the following formula (B3) as the quinonediazide-containing compound.

[ chemical formula 1]

(in the formula (B1), R^b1Each independently represents an alkyl group having 1 to 5 carbon atoms, each D independently represents a hydrogen atom or a 1, 2-diazidonaphthoquinone-5-sulfonyl group, at least one of 2+ m D represents a 1, 2-diazidonaphthoquinone-5-sulfonyl group, and each of l and m independently represents 1 or 2. )

[ chemical formula 2]

(in the formula (B2), each D is independently a hydrogen atom or a 1, 2-diazidonaphthoquinone-5-sulfonyl group, and at least one of 3D's is a 1, 2-diazidonaphthoquinone-5-sulfonyl group.)

[ chemical formula 3]

(in the formula (B3), R^b3Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R^b4Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms, each D independently represents a hydrogen atom or a 1, 2-diazidonaphthoquinone-5-sulfonyl group, and at least one of the 4D groups represents a 1, 2-diazidonaphthoquinone-5-sulfonyl group. )

In the formula (B1), R^b1Each independently represents an alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms may be linear or branched. Preferred specific examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butylT-butyl, n-pentyl, isopentyl, and neopentyl, and the like.

As R^b1Methyl and ethyl are preferred, and methyl is more preferred.

The average proportion (average esterification rate) of the 1, 2-diazidonaphthoquinone-5-sulfonyl group in the quinonediazide ester compound represented by formula (B1) in D is preferably 40% or more and 60% or less, and more preferably 50% or more and 55% or less, from the viewpoint of facilitating the solubility and sensitivity of the positive photosensitive resin composition in a developer to fall within an appropriate range.

The average proportion (average esterification rate) of the 1, 2-diazidonaphthoquinone-5-sulfonyl group in the quinonediazide ester compound represented by formula (B2) in D is preferably 65% or more and 85% or less, more preferably 70% or more and 75% or less, from the viewpoint of facilitating the solubility and sensitivity of the positive photosensitive resin composition in a developer to fall within an appropriate range.

In the formula (B3), R^b3Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms may be linear or branched. Preferred examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, and a n-hexyl group.

As R^b3Preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

In the formula (B3), R^b4Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms.

An alkyl group having 1 to 6 carbon atoms and R as the radical^b3The alkyl groups of (a) are the same.

Specific examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentoxy group, an isopentoxy group, a neopentoxy group, and a n-hexoxy group.

Specific examples of the cycloalkyl group having 3 to 6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Among these, cyclohexyl is preferable.

When the compound represented by formula (B1), the compound represented by formula (B2), and the compound represented by formula (B3) are used in combination, the ratio M1/(M2+ M3) of the mass M1 of the compound represented by formula (B1) to the total (M2+ M3) of the mass M2 of the compound represented by formula (B2) and the mass M3 of the compound represented by formula (B3) is preferably 30/70 or more and 70/30 or less, and more preferably 40/60 or more and 60/40 or less.

The ratio M2/M3 of the mass M2 of the compound represented by formula (B2) to the mass M3 of the compound represented by formula (B3) is preferably 30/70 or more and 70/30 or less, and more preferably 40/60 or more and 60/40 or less.

The content of the quinonediazido group-containing compound (B) is preferably in the following range from the viewpoint of the sensitivity of the positive photosensitive resin composition. The lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, per 100 parts by mass of the Novolac resin (a). The upper limit is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 30 parts by mass or less, per 100 parts by mass of the Novolac resin (a).

< sensitizer (C) >)

The positive photosensitive resin composition contains a sensitizer (C). The sensitizer (C) is a compound having a phenolic hydroxyl group with a molecular weight of 1000 or less.

The positive photosensitive resin composition easily realizes both a good cross-sectional shape and high sensitivity of a patterned resist film by comprising a Novolac resin (a), a quinonediazide group-containing compound (B), a sensitizer (C), and a phenolic hydroxyl group-containing resin (D) in combination.

Preferred examples of the compound that can be used as the sensitizer (C) include various phenolic hydroxyl group-containing compounds described with respect to the quinonediazido group-containing compound (B).

That is, preferable specific examples of the sensitizer (C) include: polyhydroxy benzophenones such as 2,3, 4-trihydroxybenzophenone, 2,4,4 ' -trihydroxybenzophenone, 2,4, 6-trihydroxybenzophenone, 2,3, 4-trihydroxy-2 ' -methylbenzophenone, 2,3,4,4 ' -tetrahydroxybenzophenone, 2 ', 4,4 ' -tetrahydroxybenzophenone, 2,3 ', 4,4 ', 6-pentahydroxybenzophenone, 2 ', 3,4,4 ' -pentahydroxybenzophenone, 2 ', 3,4, 5-pentahydroxybenzophenone, 2,3 ', 4,4 ', 5 ', 6-hexahydroxybenzophenone, 2,3,3 ', 4,4 ', 5 ' -hexahydroxybenzophenone, and 2,3,3 ', 4,4 ', 5 ' -hexahydroxybenzophenone; bis [ (poly) hydroxyphenyl ] ethylidene } bisphenols such as 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 '- {1- [4- [ 2- (4-hydroxyphenyl) -2-propyl ] phenyl ] ethylidene } bisphenol, and 3, 3' -dimethyl- {1- [4- [ 2- (3-methyl-4-hydroxyphenyl) -2-propyl ] phenyl ] ethylidene } bisphenol Alkanes; tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3, 5-dimethylphenyl) -4-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -4-hydroxyphenyl methane, bis (4-hydroxy-3, 5-dimethylphenyl) -2-hydroxyphenyl methane, tris (hydroxyphenyl) methanes such as bis (4-hydroxy-2, 5-dimethylphenyl) -2-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -3, 4-dihydroxyphenyl methane, and bis (4-hydroxy-3, 5-dimethylphenyl) -3, 4-dihydroxyphenyl methane, or methyl-substituted products thereof; bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenyl methane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenyl methane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenyl methane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenyl methane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenyl methane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenyl methane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenyl methane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenyl methane, bis (3-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenyl methane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenyl methane, bis (3-cyclohexyl-4-hydroxy-2-hydroxyphenyl) methane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -2-hydroxyphenylmethane, and bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane Bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes such as alkanes and methyl-substituted compounds thereof; hydroxyl group-containing compounds such as phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, catechol, pyrogallol monomethyl ether, pyrogallol-1, 3-dimethyl ether, and gallic acid.

The content of the sensitizer (C) is not particularly limited within a range not impairing the object of the present invention. The content of the sensitizer (C) is preferably 10 parts by mass or more and 30 parts by mass or less, more preferably 13 parts by mass or more and 27 parts by mass or less, and further preferably 15 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the Novolac resin (a), from the viewpoint of easily obtaining desired effects regarding the sectional shape and sensitivity of the resist film.

< resin (D) containing phenolic hydroxyl group >

The positive photosensitive resin composition contains a resin (D) containing a phenolic hydroxyl group. The phenolic hydroxyl group-containing resin (D) is a resin having a weight average molecular weight of more than 1000 other than the Novolac resin (a).

By including the Novolac resin (a) and the sensitizer (C) and also including the following predetermined amount of the phenolic hydroxyl group-containing resin (D), the positive photosensitive resin composition can exhibit appropriate solubility in a developer, and can easily achieve both a good cross-sectional shape and high sensitivity of a patterned resist film without impairing the strength and the like of the resist film.

The content of the phenolic hydroxyl group-containing resin (D) is 0.5 parts by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 9 parts by mass or less, and still more preferably 2 parts by mass or more and 8 parts by mass or less, with respect to 100 parts by mass of the Novolac resin (a).

The phenolic hydroxyl group-containing resin (D) is not particularly limited as long as it has a weight average molecular weight of more than 1000 and is a resin other than the Novolac resin (a). Preferred examples of the resin containing a phenolic hydroxyl group (D) include resins containing a structural unit derived from hydroxystyrene which may have a substituent and/or a structural unit derived from (meth) acrylate which may have a hydroxyphenyl group which may have a substituent.

When the phenolic hydroxyl group-containing resin (D) is a resin containing a structural unit derived from hydroxystyrene which may have a substituent and/or a structural unit derived from (meth) acrylate which may have a hydroxyphenyl group which may have a substituent, the amount of the structural unit having a phenolic hydroxyl group in the resin is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, and most preferably 100 mol% based on the total structural units.

As the structural unit derived from hydroxystyrene which may have a substituent, a structural unit represented by the following formula (D1) is preferable.

[ chemical formula 4]

(in the formula (D1), R^d1Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R^d2An alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. n is an integer of 0 to 4 inclusive. When n is an integer of 2 to 4 inclusive, a plurality of R^d2May be the same or different. )

The alkyl group having 1 to 6 carbon atoms is, for example, a linear or branched alkyl group having 1 to 6 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, and a neopentyl group.

The alkoxy group having 1 to 6 carbon atoms is, for example, a linear or branched alkoxy group having 1 to 6 carbon atoms. Examples of the straight-chain or branched alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a n-pentyloxy group, an isopentyloxy group, and a neopentyloxy group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Preferred examples of the monomer providing the structural unit represented by the formula (D1) include 4-hydroxystyrene, 3-hydroxystyrene, 2-hydroxystyrene, α -methyl-4-hydroxystyrene, α -methyl-3-hydroxystyrene, α -methyl-2-hydroxystyrene, α -ethyl-4-hydroxystyrene, α -ethyl-3-hydroxystyrene, α -ethyl-2-hydroxystyrene and the like. Among these, 4-hydroxystyrene, 3-hydroxystyrene, α -methyl-4-hydroxystyrene, and α -methyl-3-hydroxystyrene are preferable, and 4-hydroxystyrene, and α -methyl-4-hydroxystyrene are more preferable.

As the structural unit derived from a (meth) acrylate having a hydroxyphenyl group which may have a substituent, a structural unit represented by the following formula (D2) is preferable.

[ chemical formula 5]

(in the formula (D2), R^d2And n and R in the formula (D1)^d2And n are the same. R^d3Is a hydrogen atom or a methyl group. R^d4A single bond, or an alkylene group having 1 to 4 carbon atoms. )

With respect to as R^d4Examples of the alkylene group of (a) include a methylene group, an ethane-1, 2-diyl group (ethylene group), an ethane-1, 1-diyl group, a propane-1, 3-diyl group, a propane-1, 2-diyl group, a propane-2, 2-diyl group, a propane-3, 3-diyl group and a butane-1, 4-diyl group. Among these, methylene, ethylene, propane-1, 3-diyl and butane-1, 4-diyl are preferable, and methylene and ethylene are more preferable.

Preferred specific examples of the monomer providing the structural unit represented by the formula (D2) include acrylic acid esters having phenolic hydroxyl groups such as 4-hydroxyphenyl acrylate, 3-hydroxyphenyl acrylate, 2-hydroxyphenyl acrylate, 4-hydroxybenzyl acrylate, 3-hydroxybenzyl acrylate, 2-hydroxybenzyl acrylate, 4-hydroxyphenyl ethyl acrylate, 3-hydroxyphenyl ethyl acrylate and 2-hydroxyphenyl ethyl acrylate, 4-hydroxyphenyl methacrylate, 3-hydroxyphenyl methacrylate, 2-hydroxyphenyl methacrylate, 4-hydroxybenzyl methacrylate, 3-hydroxybenzyl methacrylate, 2-hydroxybenzyl methacrylate, 4-hydroxybenzyl methacrylate, 3-hydroxyphenyl ethyl acrylate, 3-hydroxy benzyl acrylate, and the like, And phenolic hydroxyl group-containing methacrylates such as 2-hydroxyphenylethyl methacrylate.

Among these, 4-hydroxyphenyl acrylate, 3-hydroxyphenyl acrylate, 4-hydroxybenzyl acrylate, 3-hydroxybenzyl acrylate, 4-hydroxybenzyl methacrylate, 3-hydroxyphenyl methacrylate, 4-hydroxybenzyl methacrylate, and 3-hydroxybenzyl methacrylate are preferable, and examples thereof include 4-hydroxyphenyl acrylate, 4-hydroxybenzyl acrylate, 4-hydroxyphenyl methacrylate, and 4-hydroxybenzyl methacrylate.

When the phenolic hydroxyl group-containing resin (D) is a polymer of a monomer having an unsaturated bond, the phenolic hydroxyl group-containing resin (D) may be a copolymer of a monomer having a phenolic hydroxyl group and another monomer having no phenolic hydroxyl group.

Examples of the other monomer include known radical polymerizable compounds and anionic polymerizable compounds. Examples of such polymerizable compounds include: monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond such as 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; dicarboxylic diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α -methylstyrene, chlorostyrene, chloromethylstyrene, and vinyltoluene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated dienes such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide; and so on.

The resin (D) containing a phenolic hydroxyl group described above is preferably a resin having a structural unit derived from hydroxystyrene which may have a substituent, more preferably a resin having a structural unit derived from hydroxystyrene, still more preferably a homopolymer of hydroxystyrene, and particularly preferably a homopolymer of 4-hydroxystyrene, in view of easily obtaining the desired effect by using the resin containing a phenolic hydroxyl group.

As described above, the weight average molecular weight of the phenolic hydroxyl group-containing resin (D) is not particularly limited, as long as it exceeds 1000. The weight average molecular weight of the phenolic hydroxyl group-containing resin (D) is preferably 3000 or more and 15000 or less, more preferably 4000 or more and 13000 or less, and still more preferably 5000 or more and 10000 or less, from the viewpoint of easily obtaining a positive photosensitive resin composition particularly suitable for solubility in a developer.

< other ingredients >

The positive type composition may contain various additives such as a colorant, a sensitizer, an adhesion improver, a surfactant, and a plasticizer within a range not to impair the object of the present invention.

Sensitizers

The sensitizer is not particularly limited, and may be arbitrarily selected from sensitizers generally used in positive photosensitive resin compositions. Examples of the sensitizer include compounds having a phenolic hydroxyl group with a molecular weight of 1000 or less.

Adhesion improver

The adhesion improver may be appropriately selected from materials capable of improving adhesion between the patterned resist film and the surface on which the resist film is formed. For example, a hydroxyalkyl nitrogen-containing heterocyclic compound such as 2-hydroxyethylpyridine can be used as the adhesion improver.

Surfactants

The positive photosensitive resin composition may contain a surfactant in order to improve coatability, defoaming property, leveling property, and the like. As the surfactant, for example, BM-1000, BM-1100 (manufactured by BM CHEMIE corporation, Japan, Inc. ' BM ケミー Co.), MEGAFACE (manufactured by Japan, Inc. ' メガファック ') F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F183 (manufactured by Japan ink chemical industry Co., Ltd.), Fluorad (Japanese, Inc. ' フロラード) FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (manufactured by You3M Co., Ltd.), Surflon (Japanese, Japan, Inc. ' サーフロン) S-112, commercially available silicon or fluorine surfactants such as Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (manufactured by Asahi glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (manufactured by Toray Silicone Co., Ltd.), BYK-310, BYK-330 (manufactured by BYK-Chemie Japan Co., Ltd.).

The content of the surfactant is preferably 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the Novolac resin (a).

< solvent >

In the positive photosensitive resin composition, the respective components are preferably dissolved in an appropriate solvent and used in the form of a solution. Examples of such solvents include: ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; aromatic hydrocarbons such as toluene and xylene; cyclic ethers such as dioxane; and esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxoacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate; and so on. These solvents may be used alone or in combination of two or more.

The content of the solvent in the positive photosensitive resin composition is appropriately adjusted in consideration of the viscosity and coatability of the positive photosensitive resin composition. Specifically, the solvent is used so that the solid content concentration of the positive photosensitive resin composition is preferably 5 mass% or more and 50 mass% or less, more preferably 10 mass% or more and 30 mass% or less.

< method for producing positive photosensitive resin composition >

The positive photosensitive resin composition can be prepared by: the above components are blended at a predetermined ratio, and then mixed and stirred by a usual method. Further, filtration may be performed using a mesh, a membrane filter, or the like as necessary.

Method for Forming patterned resist film

The patterned resist film may be formed by a method including the steps of:

a step of coating the positive photosensitive resin composition on a substrate to form a coating film;

and developing the exposed coating film with a developer.

The application of the positive photosensitive resin composition to the substrate is performed using a spin coater, a roll coater, a spray coater, a slit coater, or the like. The coating device is not limited to these. Generally, the coating film is dried by a method such as heating. The drying method may be, for example, any of the following methods: (1) a method of drying the coating film at a temperature of 80 ℃ to 120 ℃ for 60 seconds to 120 seconds by a hot plate; (2) a method of leaving the coating film at room temperature for several hours to several days; (3) a method of removing the solvent by placing the coating film in a hot air heater or an infrared heater for several tens of minutes to several hours. The thickness of the coating film after drying is not particularly limited as necessary, but is preferably about 1.0 μm to 5.0 μm.

The kind of the substrate is not particularly limited. The positive photosensitive resin composition is excellent in sensitivity and therefore can be easily applied to a large-area substrate. Therefore, as a suitable substrate, a substrate for a display such as a liquid crystal display or an organic EL display can be mentioned. Examples of the substrate for these displays include a glass plate provided with a wiring such as a transparent conductive circuit, and if necessary, with a black matrix, a color filter, a polarizing plate, and the like.

Next, the coating film is exposed through a mask having a predetermined pattern corresponding to the pattern shape. The exposure is performed by irradiation with active energy rays such as ultraviolet rays and excimer laser light. Examples of the light source of the active energy ray include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, and an excimer laser generator. The amount of energy radiation to be irradiated varies depending on the composition of the positive photosensitive resin composition, and may be, for example, 30 to 2000mJ/cm²Left and right.

Next, the exposed coating film is developed with a developer to form a patterned resist film. Examples of the developer include an aqueous solution of an organic base such as a tetramethylammonium hydroxide (TMAH) aqueous solution, and an aqueous solution of an inorganic base such as sodium hydroxide, potassium hydroxide, sodium metasilicate, or sodium phosphate.

After the development, the surface of the patterned resist film may be rinsed with water, an organic solvent that does not excessively dissolve the resist film, or the like. In addition, the patterned resist film may be baked as necessary.

Thereby, a patterned resist film formed of the positive photosensitive resin composition is formed. The resist film can be used as a protective film or an insulating film, and can also be used as a mask pattern for etching or a mold for plating.

[ examples ]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[ examples 1 to 10 and comparative examples 1 to 6]

In examples and comparative examples, as the Novolac resin (a) ((a) component), cresol Novolac resin (weight average molecular weight 6000) having a mass of m-cresol/p-cresol of 36/64 was used.

In examples and comparative examples, the following B-I, B-II and B-III were used as the quinonediazido group-containing compound (B) (component (B)). B-I belongs to the compounds represented by the aforementioned formula (B1). B-II belongs to the aforementioned compound represented by the formula (B2). B to III belong to the compounds represented by the aforementioned formula (B3). In addition, the average introduction rate of the quinonediazide group (which means how many moles of the substituent OD are substituted by the quinonediazide group on average) of each compound was 2.1 moles of B-I, 1.7 moles of B-II and 2.5 moles of B-III.

[ chemical formula 6]

In examples and comparative examples, the following C-I and C-II were used as the sensitizer (C) (component (C)).

C-I: a compound represented by the formula

C-II: compounds wherein D in each of the foregoing B to III is a hydrogen atom

[ chemical formula 7]

In examples and comparative examples, the following D-I and D-II were used as the phenolic hydroxyl group-containing resin (D) (component (D)).

D-I: homopolymer of 4-hydroxystyrene (weight average molecular weight 8000)

D-II: copolymer of 4-hydroxystyrene 75 mass% and styrene 25 mass% (weight average molecular weight 2500)

100 parts by mass of a Novolac resin (a), a quinonediazide group-containing compound (B) of the type and amount shown in table 1, a sensitizer (C) of the amount shown in table 1, a phenolic hydroxyl group-containing resin (D) of the type and amount shown in table 1, 2-pyridylethanol as an adhesion enhancer of the amount shown in table 1, and a surfactant BYK-310 (manufactured by BYK-Chemie) of the amount shown in table 1 were dissolved in propylene glycol monomethyl ether acetate so that the solid concentration became 24 mass%, to obtain positive photosensitive resin compositions of examples and comparative examples. Using the obtained positive photosensitive resin composition, the sensitivity, the cross-sectional shape, and the resolution were evaluated in the following manner. The evaluation results are shown in Table 1.

< sensitivity >

A sample of the positive photosensitive resin composition was coated on an 8-inch Si wafer using a spin coater to form a coating film. The coating film was dried at 110 ℃ for 90 seconds with a Direct Hot Plate (DHP) to form a resist coating film having a thickness of 1.5 μm.

Next, exposure was performed using FPA-5510iv (product name, manufactured by Canon corporation, NA 0.12) through a test pattern mask (reticle) on which a mask pattern was drawn for realizing a 1.3 μm line and space pattern.

The exposed resist film was brought into contact with a 2.38 mass% aqueous tetramethylammonium hydroxide (TMAH) solution at 23 ℃ for 65 seconds, and developed. The resist pattern obtained was washed with water for 30 seconds and spin-dried.

The shape of the obtained resist pattern was observed by an SEM photograph, and the exposure amount at which the pattern size became 1.3 μm was confirmed. The sensitivity was evaluated based on the exposure dose at which the pattern size became 1.30 μm according to the following criteria.

Very good: the exposure amount for the pattern size to be 1.3 μm is less than 45mJ/cm²。

Good: the exposure dose was 45mJ/cm with the pattern size of 1.3 μm²Above and less than 55mJ/cm²。

X: the exposure dose for the pattern size to be 1.3 μm was 55mJ/cm²The above.

< cross-sectional shape >

The cross-sectional shapes of the 1.3 μm line and gap patterns obtained in the sensitivity evaluation were observed by SEM photograph, and the cross-sectional shapes were evaluated according to the following criteria.

Very good: rectangular shape

Good: a T-shaped top having a resist pattern with a width near the surface opposite to the substrate larger than a width near the center of the resist pattern in the height direction

X: without a head (Japanese: head き (section shape is nearly triangular pattern shape) and し)

< resolution >

Using the same method as the above-described sensitivity evaluation, exposure was performed at an exposure amount capable of reproducing the 1.3 μm line and space pattern in size using a mask for realizing the 1.3 μm line and space pattern, a mask for realizing the 1.2 μm line and space pattern, and a mask for realizing the 1.1 μm line and space pattern, to form the line and space pattern. The obtained line and space patterns were observed in an SEM photograph, and the resolution was evaluated according to the following criteria. When the evaluation of the cross-sectional shape is x, the evaluation is difficult, and therefore the resolution is not evaluated.

1.3: line and space patterns of 1.3 μm can be resolved, but line and space patterns of 1.2 μm cannot be resolved.

1.2: line and space patterns of 1.2 μm can be resolved, but line and space patterns of 1.1 μm cannot be resolved.

As is apparent from table 1, the positive photosensitive resin composition comprising the Novolac resin (a), the quinonediazide group-containing compound (B), the sensitizer (C) satisfying the predetermined requirements, and the phenolic hydroxyl group-containing resin (D) satisfying the predetermined requirements and in an amount within a predetermined range is excellent in sensitivity and can provide a patterned resist film having a good cross-sectional shape.

Claims

1. A positive photosensitive resin composition comprising a Novolac resin (A), a quinonediazido group-containing compound (B), a sensitizer (C), and a phenolic hydroxyl group-containing resin (D),

2. The positive photosensitive resin composition according to claim 1, wherein the phenolic hydroxyl group-containing resin (D) comprises a structural unit derived from hydroxystyrene which may have a substituent and/or a structural unit derived from (meth) acrylate which may have a hydroxyphenyl group which may have a substituent.

3. The positive photosensitive resin composition according to claim 2, wherein the phenolic hydroxyl group-containing resin (D) is a homopolymer of hydroxystyrene.

4. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the weight average molecular weight of the phenolic hydroxyl group-containing resin (D) is 3000 or more and 15000 or less.

5. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the content of the sensitizer (C) is 10 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the Novolac resin (A).

6. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the quinonediazide group-containing compound (B) comprises, in combination, a compound represented by the following formula (B1), a compound represented by the following formula (B2), and a compound represented by the following formula (B3),

[ chemical formula 1]

In the formula (B1), R^b1Each independently an alkyl group having 1 to 5 carbon atoms, each D independently a hydrogen atom or a 1, 2-diazidonaphthoquinone-5-sulfonyl group, at least one of 2+ m D groups being a 1, 2-diazidonaphthoquinone-5-sulfonyl group, each l and m independently being 1 or 2,

[ chemical formula 2]

In the formula (B2), D's are each independently a hydrogen atom or a 1, 2-diazidonaphthoquinone-5-sulfonyl group, at least one of 3D's is a 1, 2-diazidonaphthoquinone-5-sulfonyl group,

[ chemical formula 3]

In the formula (B3), R^b3Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R^b4Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms, each D independently represents a hydrogen atom or a 1, 2-diazidonaphthoquinone-5-sulfonyl group, and at least one of the 4D groups represents a 1, 2-diazidonaphthoquinone-5-sulfonyl group.

7. A method for forming a patterned resist film, comprising the steps of:

a step of forming a coating film by coating the positive photosensitive resin composition according to any one of claims 1 to 6 on a substrate;

exposing the coating film in a position-selective manner; and the combination of (a) and (b),

and developing the exposed coating film with a developer.

8. A patterned resist film comprising the positive photosensitive resin composition according to any one of claims 1 to 6.