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

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 present invention aims to provide a positive photosensitive resin composition that 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. The solution is to include in the positive photosensitive resin composition: a Novolac resin (A); a compound (B) containing a quinonediazide group; a sensitizer (C) that is a compound having a molecular weight of 1000 or less and having a phenolic hydroxyl group; and a phenolic hydroxyl group-containing resin (D) in an amount within a specified range, wherein the resin (D) is a resin other than the Novolac resin (A) and has a weight-average molecular weight exceeding 1000.

Description

Technical Field

[0001] The present invention relates to a positive photosensitive resin composition, a method for forming a patterned resist film, and a patterned resist film. Background Art

[0002] Known methods for forming wirings and terminals on a substrate include etching a metal layer using a resist pattern as a mask pattern, and performing electroplating using a resist pattern as a mold pattern for electroplating.

[0003] The method for forming a resist pattern when forming wiring and terminals on a substrate generally involves using a dry film made from a negative-working photosensitive composition to form a photosensitive composition layer on the substrate, which is then exposed and developed. However, using a negative-working photosensitive composition presents problems such as insufficient resolution and difficulty in peeling the resist pattern from the substrate.

[0004] As a method for solving the above-mentioned problems, there is a method of forming a resist pattern using a positive photosensitive composition that has good resolution and is relatively easily peeled from a substrate.

[0005] As a positive photosensitive composition that can be used to form wiring, terminals, etc. made of metal, for example, a photosensitive composition containing an alkali-soluble Novolac resin such as cresol Novolac resin, a photosensitizer, and a benzotriazole compound is known (see Patent Document 1).

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 2010-176012 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] When forming fine wiring and terminals, it is desirable to use a photosensitive composition that can form a resist pattern with a nearly rectangular cross-sectional shape and that has high sensitivity. However, with the positive-working photosensitive composition described in Patent Document 1, it is difficult to simultaneously achieve a good cross-sectional shape and high sensitivity in the resist pattern.

[0011] The present invention has been made in view of the above-mentioned problems, and its object is to provide a positive photosensitive resin composition that 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 from the above-mentioned positive photosensitive resin composition.

[0012] Means for solving problems

[0013] The inventors of the present application have discovered that the above-mentioned problems can be solved by including in a positive-type photosensitive resin composition: a Novolac resin (A); a quinonediazide group-containing compound (B); a sensitizer (C) which is a compound having a molecular weight of 1000 or less and having a phenolic hydroxyl group; and a phenolic hydroxyl group-containing resin (D) in an amount within a specified range, wherein the resin (D) is a resin other than the Novolac resin (A) and has a weight-average molecular weight exceeding 1000. The inventors have thus completed the present invention. Specifically, the present invention provides the following solutions.

[0014] A first embodiment of the present invention is a positive photosensitive resin composition comprising a Novolac resin (A), a quinonediazide group-containing compound (B), a sensitizer (C), and a phenolic hydroxyl group-containing resin (D).

[0015] The sensitizer (C) is a compound having a phenolic hydroxyl group and a molecular weight of 1000 or less.

[0016] The phenolic hydroxyl group-containing resin (D) is a resin other than the Novolac resin (A) having a weight average molecular weight exceeding 1000.

[0017] 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 relative to 100 parts by mass of the Novolac resin (A).

[0018] A second embodiment of the present invention is a method for forming a patterned resist film, comprising the following steps:

[0019] a step of applying the positive photosensitive resin composition according to the first embodiment to a substrate to form a coating film;

[0020] a step of exposing the coating film in a position-selective manner; and

[0021] A step of developing the exposed coating film with a developer.

[0022] A third aspect of the present invention is a patterned resist film formed from the positive photosensitive resin composition according to the first aspect.

[0023] Effects of the Invention

[0024] According to the present invention, there are provided a positive photosensitive resin composition that 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. DETAILED DESCRIPTION

[0025] Positive photosensitive resin composition

[0026] The positive photosensitive resin composition includes a Novolac resin (A), a quinonediazide group-containing compound (B), a sensitizer (C), and a phenolic hydroxyl group-containing resin (D).

[0027] The sensitizer (C) is a compound having a phenolic hydroxyl group and a molecular weight of 1,000 or less.

[0028] The phenolic hydroxyl group-containing resin (D) is a resin having a weight average molecular weight exceeding 1,000 other than the Novolac resin (A).

[0029] 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 relative to 100 parts by mass of the Novolac resin (A).

[0030] The positive photosensitive resin composition having the above-described structure can achieve both a good cross-sectional shape of the patterned resist film and high sensitivity.

[0031] Hereinafter, essential or optional components contained in the positive photosensitive resin composition will be described.

[0032] Novolac resin (A)

[0033] As the Novolac resin (A), various Novolac resins conventionally incorporated into positive-type photosensitive resin compositions can be used. Novolac resin (A) is preferably obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter referred to as "phenol") with an aldehyde in the presence of an acid catalyst.

[0034] Phenols

[0035] 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; 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and alkylphenols such as p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; polyphenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglucinol; alkylpolyphenols such as alkylresorcinol, alkylcatechol, and alkylhydroquinone (all alkyl groups have 1 to 4 carbon atoms); α-naphthol; β-naphthol; hydroxybiphenyl; and bisphenol A. These phenols may be used alone or in combination of two or more.

[0036] Among these phenols, m-cresol and p-cresol are preferred, and a combination of m-cresol and p-cresol is more preferred. In this case, by adjusting the ratio of the two, various properties such as the sensitivity of the positive-type photosensitive resin composition and the heat resistance of the resist film formed can be adjusted. The mixing ratio of m-cresol to p-cresol is not particularly limited, but is preferably 3 / 7 or more and 8 / 2 or less, based on the mass ratio of m-cresol to p-cresol. When the ratio of m-cresol is 3 / 7 or more, the sensitivity of the positive-type photosensitive resin composition can be improved. When the ratio of m-cresol is 8 / 2 or less, the heat resistance of the resist film formed using the photosensitive resin composition can be improved.

[0037] ·Aldehydes

[0038] Examples of the aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

[0039] Acid catalyst

[0040] 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, diethylsulfuric 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.

[0041] Molecular weight

[0042] From the viewpoints of developability and resolution of the positive-type photosensitive resin composition, the weight average molecular weight (Mw; hereinafter also referred to as "weight average molecular weight") of the Novolac resin (A) in terms of polystyrene conversion is preferably 1,000 or greater, more preferably 2,000 or greater, and even more preferably 3,000 or greater. The weight average molecular weight of the Novolac resin (A) is preferably 50,000 or less, more preferably 40,000 or less, even more preferably 30,000 or less, and even more preferably 20,000 or less.

[0043] 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.

[0044] In this specification, the weight average molecular weight Mw and the number average molecular weight Mn can be defined as relative values ​​in terms of polystyrene in GPC (gel permeation chromatography) measurement.

[0045] When a plurality of Novolac resins (A) are used, the dispersion degree can be determined based on the obtained spectrum by performing GPC (gel permeation chromatography) measurement on the combination of the plurality of Novolac resins (A).

[0046] As the Novolac resin (A), at least two resins having different weight-average molecular weights in terms of polystyrene can be used in combination. By using these resins in combination, it is possible to impart excellent properties such as developability, resolution, and film-forming properties to the positive-type photosensitive resin composition.

[0047] Regarding the Novolac resin (A), there are no particular limitations on the combination of resins having different weight-average molecular weights. Preferred combinations include a resin having a low weight-average molecular weight of 1,000 to 10,000 and a resin having a high weight-average molecular weight of 5,000 to 50,000. More preferred combinations include a resin having a low weight-average molecular weight of 2,000 to 8,000 and a resin having a high weight-average molecular weight of 8,000 to 40,000. Further preferred combinations include a resin having a low weight-average molecular weight of 3,000 to 7,000 and a resin having a high weight-average molecular weight of 10,000 to 20,000.

[0048] When using a combination of resins having different weight-average molecular weights as the Novolac resin (A), the content of each resin is not particularly limited. The content of the resin with the lower weight-average molecular weight in the total amount of the Novolac resin (A) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. On the other hand, the content of the resin with the lower weight-average molecular weight in the total amount of the Novolac resin (A) is preferably 50% by mass or less, more preferably 40% by mass or less.

[0049] The ratio of the mass of the Novolac resin (A) to the total 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 quinonediazide group-containing compound (B), the sensitizer (C), and the phenolic hydroxyl group-containing resin (D).

[0050] The mass ratio of the Novolac resin (A) to the total solid content of the positive photosensitive resin composition is preferably 40% by mass or more and 80% by mass or less, more preferably 45% by mass or more and 75% by mass or less, and further preferably 50% by mass or more and 70% by mass or less.

[0051] <Quinonediazide group-containing compound (B)>

[0052] The positive-type photosensitive resin composition contains a quinonediazide group-containing compound (B). The quinonediazide group-containing compound (B) can be appropriately selected from compounds containing a quinonediazide group that have been incorporated into various conventional positive-type photosensitive resin compositions.

[0053] Preferred specific examples of the compound (B) containing a quinonediazide group include complete ester compounds, partial ester compounds, amides, or partial amides of the following substances with sulfonic acids containing a quinonediazide group: 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone. Polyhydroxybenzophenones such as hydroxybenzophenone, 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'-hexahydroxybenzophenone; bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2 Bis((poly)hydroxyphenyl)alkanes such as tris(4-hydroxyphenyl)methane, bis ... tris(hydroxyphenyl)methanes such as bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, and bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, or their methyl-substituted products;Bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3- Bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methanes or methyl-substituted products thereof, such as 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; compounds having a hydroxyl group or an amino group, such as phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, catechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine, and 4,4'-diaminobenzophenone; and pyrogallol-acetone resins. These quinonediazide group-containing compounds (B) may be used alone or in combination of two or more. ;

[0054] The sulfonic acid containing a quinonediazide group used as the compound (B) containing a quinonediazide group is not particularly limited. For example, naphthoquinonediazidesulfonic acids such as naphthoquinone-1,2-diazide-5-sulfonic acid and naphthoquinone-1,2-diazide-4-sulfonic acid; and o-anthraquinonediazidesulfonic acid are mentioned. Among these, naphthoquinonediazidesulfonic acid is preferred. The sulfonic acid containing a quinonediazide group, preferably the ester compound of naphthoquinonediazidesulfonic acid, is well soluble in solvents commonly used when using a positive-type composition in the form of a solution and has good compatibility with the Novolac resin (A). When these compounds are combined as the compound (B) containing a quinonediazide group with a positive-type photosensitive resin composition, a highly sensitive positive-type photosensitive resin composition can be easily obtained.

[0055] The method for producing the ester compound as the quinonediazide group-containing compound (B) is not particularly limited. For example, the following method can be mentioned: a quinonediazide group-containing sulfonic acid is added in the form of a sulfonyl chloride such as naphthoquinone-1,2-diazide-sulfonyl chloride, and the mixture is condensed in a solvent such as dioxane in the presence of a base such as triethanolamine, alkali carbonate, or alkali bicarbonate to achieve complete or partial esterification.

[0056] From the perspective of good sensitivity and resolution of the positive photosensitive resin composition and the ease of using the positive photosensitive resin composition to form a patterned resist film with a good shape, it is also preferred that the positive photosensitive resin composition contain 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) in combination as a compound containing a quinonediazide group.

[0057] [Chemical Formula 1]

[0058]

[0059] (In formula (B1), R b1 Each independently represents an alkyl group having 1 to 5 carbon atoms, each D independently represents a hydrogen atom or a 1,2-diazide naphthoquinone-5-sulfonyl group, at least one of the 2+m Ds is a 1,2-diazide naphthoquinone-5-sulfonyl group, and l and m independently represent 1 or 2.

[0060] [Chemical Formula 2]

[0061]

[0062] (In formula (B2), D is independently a hydrogen atom or a 1,2-diazide naphthoquinone-5-sulfonyl group, and at least one of the three Ds is a 1,2-diazide naphthoquinone-5-sulfonyl group.)

[0063] [Chemical Formula 3]

[0064]

[0065] (In formula (B3), R b3 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R b4 Each of the four Ds is independently 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, and each of the four Ds is independently a hydrogen atom or a 1,2-diazide naphthoquinone-5-sulfonyl group, and at least one of the four Ds is a 1,2-diazide naphthoquinone-5-sulfonyl group.

[0066] In 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-butyl, tert-butyl, n-pentyl, isopentyl, and neopentyl.

[0067] As R b1 , preferably methyl and ethyl, more preferably methyl.

[0068] From the perspective of easily ensuring that the solubility and sensitivity of the positive photosensitive resin composition in the developer are within an appropriate range, the average ratio (average esterification rate) of D in the quinone diazide ester represented by formula (B1) being a 1,2-naphthoquinone diazide-5-sulfonyl group is preferably 40% or more and 60% or less, and more preferably 50% or more and 55% or less.

[0069] From the perspective of easily ensuring that the solubility and sensitivity of the positive photosensitive resin composition in the developer are within an appropriate range, the average ratio (average esterification rate) of D in the quinone diazide ester represented by formula (B2) being a 1,2-naphthoquinone diazide-5-sulfonyl group is preferably 65% ​​or more and 85% or less, and more preferably 70% or more and 75% or less.

[0070] In formula (B3), R b3 Each 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 specific examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and n-hexyl.

[0071] As R b3 , preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0072] In formula (B3), R b4 Each is independently 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.

[0073] The alkyl group having 1 or more and 6 or less carbon atoms and the alkyl group as R b3 The alkyl groups are the same.

[0074] Specific examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy, and n-hexoxy.

[0075] Specific examples of the cycloalkyl group having 3 to 6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Among these, cyclohexyl is preferred.

[0076] When a compound represented by formula (B1), a compound represented by formula (B2), and a 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), the mass M2 of the compound represented by formula (B2), and the mass M3 of the compound represented by formula (B3) (M2+M3) is preferably greater than 30 / 70 and less than 70 / 30, and more preferably greater than 40 / 60 and less than 60 / 40.

[0077] 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.

[0078] From the perspective of the sensitivity of the positive-type photosensitive resin composition, the content of the quinonediazide group-containing compound (B) is preferably within the following range. Regarding the lower limit, it is preferably 5 parts by mass or greater, and more preferably 10 parts by mass or greater, relative to 100 parts by mass of the Novolac resin (A). Regarding the upper limit, it is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less, relative to 100 parts by mass of the Novolac resin (A).

[0079] <Sensitizer (C)>

[0080] The positive photosensitive resin composition contains a sensitizer (C). The sensitizer (C) is a compound having a phenolic hydroxyl group and a molecular weight of 1,000 or less.

[0081] The positive photosensitive resin composition, by combining a Novolac resin (A), a quinonediazide group-containing compound (B), a sensitizer (C), and a phenolic hydroxyl group-containing resin (D), can easily achieve both a good cross-sectional shape of the patterned resist film and high sensitivity.

[0082] Preferred examples of the compound that can be used as the sensitizer (C) include the various phenolic hydroxyl group-containing compounds described for the quinonediazide group-containing compound (B).

[0083] That is, preferred specific examples of the sensitizer (C) include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 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. Benzophenone, 2,2',3,4,5-pentahydroxybenzophenone, 2,3',4,4',5',6-hexahydroxybenzophenone, 2,3,3',4,4',5'-hexahydroxybenzophenone and other polyhydroxybenzophenones; 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, Bis((poly)hydroxyphenyl)alkanes such as 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 4,4'-{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; tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-4 tris(hydroxyphenyl)methanes or their methyl substitutes such as bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, and bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane;Bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-3-hydroxyphenylmethane Bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methanes or their methyl-substituted products, such as phenylmethane, 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; compounds having a hydroxy group, such as phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, catechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, and gallic acid.

[0084] The content of the sensitizer (C) is not particularly limited within a range not impairing the purpose of the present invention. From the perspective of easily achieving the desired effects related to the cross-sectional shape and sensitivity of the resist film, the content of the sensitizer (C) is preferably 10 parts by mass to 30 parts by mass, more preferably 13 parts by mass to 27 parts by mass, and even more preferably 15 parts by mass to 20 parts by mass, relative to 100 parts by mass of the Novolac resin (A).

[0085] <Resin containing phenolic hydroxyl group (D)>

[0086] The positive photosensitive resin composition contains a phenolic hydroxyl group-containing resin (D). The phenolic hydroxyl group-containing resin (D) is a resin having a weight average molecular weight exceeding 1000 other than the Novolac resin (A).

[0087] By including the phenolic hydroxyl group-containing resin (D) in the following predetermined amount in addition to the Novolac resin (A) and the sensitizer (C), the positive-type photosensitive resin composition can exhibit moderate solubility in a developer, making it easy to simultaneously achieve a good cross-sectional shape of the patterned resist film and high sensitivity without compromising the strength of the resist film.

[0088] The content of the phenolic hydroxyl group-containing resin (D) is 0.5 to 10 parts by mass, more preferably 1 to 9 parts by mass, and even more preferably 2 to 8 parts by mass, relative to 100 parts by mass of the Novolac resin (A).

[0089] The phenolic hydroxyl group-containing resin (D) is not particularly limited as long as it has a weight-average molecular weight exceeding 1000 and is a resin other than the Novolac resin (A). Preferred examples of the phenolic hydroxyl group-containing resin (D) include resins containing a structural unit derived from a hydroxystyrene which may have a substituent and / or a structural unit derived from a (meth)acrylate having a hydroxyphenyl group which may have a substituent.

[0090] When the resin (D) containing a phenolic hydroxyl group is a resin containing a structural unit derived from a hydroxystyrene which may have a substituent and / or a structural unit derived from a (meth)acrylate having 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.

[0091] As the structural unit derived from the hydroxystyrene which may have a substituent, a structural unit represented by the following formula (D1) is preferred.

[0092] [Chemical Formula 4]

[0093]

[0094] (In formula (D1), R d1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. d2 is an 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. When n is an integer of 2 to 4, multiple R d2 Can be the same or different.)

[0095] Examples of the alkyl group having 1 to 6 carbon atoms include linear or branched alkyl groups having 1 to 6 carbon atoms. Examples of the linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and neopentyl.

[0096] Examples of the alkoxy group having 1 to 6 carbon atoms include linear or branched alkoxy groups having 1 to 6 carbon atoms. Examples of the linear or branched alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, and neopentoxy.

[0097] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0098] Preferred specific examples of monomers providing the structural unit represented by 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, and α-ethyl-2-hydroxystyrene. Among these, 4-hydroxystyrene, 3-hydroxystyrene, α-methyl-4-hydroxystyrene, and α-methyl-3-hydroxystyrene are preferred, and 4-hydroxystyrene and α-methyl-4-hydroxystyrene are more preferred.

[0099] 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 preferred.

[0100] [Chemical Formula 5]

[0101]

[0102] (In formula (D2), R d2 and n and R in formula (D1) d2 and n are the same. d3 is a hydrogen atom or a methyl group. d4 is a single bond or an alkylene group having 1 to 4 carbon atoms.

[0103] About R d4 The alkylene group includes methylene, ethane-1,2-diyl (ethylene), ethane-1,1-diyl, propane-1,3-diyl, propane-1,2-diyl, propane-2,2-diyl, propane-3,3-diyl, and butane-1,4-diyl. Among these, methylene, ethylene, propane-1,3-diyl, and butane-1,4-diyl are preferred, and methylene and ethylene are more preferred.

[0104] Preferred specific examples of the monomer providing the structural unit represented by formula (D2) include phenolic hydroxyl group-containing acrylic acid esters such as 4-hydroxyphenyl acrylate, 3-hydroxyphenyl acrylate, 2-hydroxyphenyl acrylate, 4-hydroxybenzyl acrylate, 3-hydroxybenzyl acrylate, 2-hydroxybenzyl acrylate, 4-hydroxyphenethyl acrylate, 3-hydroxyphenethyl acrylate, and 2-hydroxyphenethyl acrylate; and phenolic hydroxyl group-containing methacrylic acid esters such as 4-hydroxyphenyl methacrylate, 3-hydroxyphenyl methacrylate, 2-hydroxyphenyl methacrylate, 4-hydroxybenzyl methacrylate, 3-hydroxybenzyl methacrylate, 2-hydroxybenzyl methacrylate, 4-hydroxyphenethyl methacrylate, 3-hydroxyphenethyl methacrylate, and 2-hydroxyphenethyl methacrylate.

[0105] Among these, 4-hydroxyphenyl acrylate, 3-hydroxyphenyl acrylate, 4-hydroxybenzyl acrylate, 3-hydroxybenzyl acrylate, 4-hydroxyphenyl methacrylate, 3-hydroxyphenyl methacrylate, 4-hydroxybenzyl methacrylate, and 3-hydroxybenzyl methacrylate are preferred, and examples thereof include 4-hydroxyphenyl acrylate, 4-hydroxybenzyl acrylate, 4-hydroxyphenyl methacrylate, and 4-hydroxybenzyl methacrylate.

[0106] 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 not having a phenolic hydroxyl group.

[0107] As the above-mentioned other monomers, known free radical polymerizable compounds and anionic polymerizable compounds can be cited. In addition, as such polymerizable compounds, for example, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid can be cited; 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; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; (meth)acrylic acid alkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. (Meth)acrylates; (Meth)acrylate aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; aromatic compounds containing vinyl groups such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, and vinyltoluene; aliphatic compounds containing vinyl groups such as vinyl acetate; conjugated dienes such as butadiene and isoprene; polymerizable compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; polymerizable compounds containing chlorine such as vinyl chloride and vinylidene chloride; polymerizable compounds containing amide bonds such as acrylamide and methacrylamide; and the like.

[0108] As the resin (D) containing a phenolic hydroxyl group described above, from the perspective of easily obtaining the desired effect brought about by the use of the resin containing a phenolic hydroxyl group, a resin having a structural unit derived from hydroxystyrene which may have a substituent is preferred, a resin having a structural unit derived from hydroxystyrene is more preferred, a homopolymer of hydroxystyrene is further preferred, and a homopolymer of 4-hydroxystyrene is particularly preferred.

[0109] As described above, the weight average molecular weight of the resin (D) containing a phenolic hydroxyl group is not particularly limited as long as it exceeds 1000. From the perspective of easily obtaining a positive-type photosensitive resin composition having particularly suitable solubility in a developer, the weight average molecular weight of the resin (D) containing a phenolic hydroxyl group is preferably 3000 to 15000, more preferably 4000 to 13000, and even more preferably 5000 to 10000.

[0110] <Other ingredients>

[0111] 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 impairing the purpose of the present invention.

[0112] Sensitizer

[0113] The sensitizer is not particularly limited and can be arbitrarily selected from sensitizers generally used in positive-type photosensitive resin compositions. Examples of the sensitizer include compounds having a molecular weight of 1000 or less and a phenolic hydroxyl group.

[0114] Adhesion improver

[0115] The adhesion improver can be appropriately selected from materials that can improve the 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.

[0116] Surfactants

[0117] The positive photosensitive resin composition may contain a surfactant in order to improve coating properties, defoaming properties, leveling properties, and the like. Examples of surfactants that can be used include BM-1000 and BM-1100 (manufactured by BM Chemie Co., Ltd.), MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, and MEGAFACE F183 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, and Fluorad FC-431 (manufactured by Sumitomo 3M Co., Ltd.), and Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, and Surflon FC-170C. Commercially available silicone or fluorine-based surfactants include 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.), etc.

[0118] The content of the surfactant is preferably 0.05 parts by mass or more and 5 parts by mass or less relative to 100 parts by mass of the Novolac resin (A).

[0119] Solvents

[0120] In the case of a positive-type photosensitive resin composition, it is preferred to dissolve the above-mentioned components in an appropriate solvent and use the 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; and propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. The present invention also includes the following solvents: 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-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. These solvents may be used alone or in combination of two or more.

[0121] The solvent content in the positive photosensitive resin composition is appropriately adjusted in consideration of the viscosity and coating properties 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% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less.

[0122] <Method for preparing positive photosensitive resin composition>

[0123] The positive photosensitive resin composition can be prepared by mixing the above-mentioned components at a predetermined ratio, and then mixing and stirring them by a conventional method. Furthermore, the mixture can be filtered using a mesh, a membrane filter, or the like as needed.

[0124] 《Method for forming a patterned resist film》

[0125] The patterned resist film can be formed by a method including the following steps:

[0126] The positive photosensitive resin composition is applied to a substrate to form a coating film;

[0127] a step of exposing the coating film in a position-selective manner; and

[0128] A step of developing the exposed coating film with a developer.

[0129] The positive photosensitive resin composition is applied to the substrate using a spin coater, a roll coater, a spray coater, a slit coater, or the like. The coating apparatus is not limited thereto. Usually, the coating film is dried by heating or the like. 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°C to 120°C using a hot plate for 60 seconds to 120 seconds; (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. In addition, the thickness of the coating film after drying is not particularly limited as needed, but is preferably about 1.0 μm to 5.0 μm.

[0130] The type of substrate is not particularly limited. The aforementioned positive photosensitive resin composition has excellent sensitivity and is therefore easily applicable to large-area substrates. Therefore, suitable substrates include substrates for displays such as liquid crystal displays and organic EL displays. Examples of substrates for these displays include glass plates equipped with wiring such as transparent conductive circuits and, as needed, with a black matrix, color filters, polarizing plates, and the like.

[0131] Next, the coating film is exposed through a mask having a predetermined pattern corresponding to the pattern shape. Exposure is performed by irradiating active energy rays such as ultraviolet rays and excimer lasers. Examples of light sources for active energy rays include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, and excimer laser generators. The amount of energy irradiated varies depending on the composition of the positive photosensitive resin composition and can be, for example, 30 to 2000 mJ / cm 2 about.

[0132] Next, the exposed coating film is developed with a developer to form a patterned resist film. Examples of the developer include aqueous solutions of organic bases such as tetramethylammonium hydroxide (TMAH) aqueous solution, or aqueous solutions of inorganic bases such as sodium hydroxide, potassium hydroxide, sodium metasilicate, and sodium phosphate.

[0133] After development, the surface of the patterned resist film may be rinsed with water, an organic solvent that does not excessively dissolve the resist film, etc. In addition, the patterned resist film may be baked as needed.

[0134] Thus, a patterned resist film made of the positive photosensitive resin composition is formed. This resist film can be used as a protective film, an insulating film, an etching mask pattern, or a mold for electroplating.

[0135] [Example]

[0136] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0137] [Examples 1 to 10 and Comparative Examples 1 to 6]

[0138] In the Examples and Comparative Examples, a cresol Novolac resin (weight average molecular weight: 6000) having a m-cresol / p-cresol ratio of 36 / 64 was used as the Novolac resin (A) (component (A)).

[0139] In the Examples and Comparative Examples, the following BI, B-II, and B-III were used as the compound (B) containing a quinonediazide group (component (B)). BI belongs to the compound represented by the aforementioned formula (B1). B-II belongs to the compound represented by the aforementioned formula (B2). B-III belongs to the compound represented by the aforementioned formula (B3). It should be noted that the average introduction rate of the quinonediazide group of each compound (which refers to the average number of moles of substituents OD replaced by quinonediazide groups) is 2.1 moles for BI, 1.7 moles for B-II, and 2.5 moles for B-III.

[0140] [Chemical Formula 6]

[0141]

[0142] In Examples and Comparative Examples, the following CI and C-II were used as the sensitizer (C) (component (C)).

[0143] CI: Compound represented by the following formula

[0144] C-II: Compounds in which all D atoms in B-III are hydrogen atoms

[0145] [Chemical Formula 7]

[0146]

[0147] In Examples and Comparative Examples, the following DI and D-II were used as the phenolic hydroxyl group-containing resin (D) (component (D)).

[0148] DI: 4-hydroxystyrene homopolymer (weight average molecular weight 8000)

[0149] D-II: Copolymer of 75% by mass of 4-hydroxystyrene and 25% by mass of styrene (weight average molecular weight 2500)

[0150] 100 parts by mass of Novolac resin (A), a quinonediazide group-containing compound (B) of the type and amount listed in Table 1, a sensitizer (C) of the amount listed in Table 1, a phenolic hydroxyl group-containing resin (D) of the type and amount listed in Table 1, 2-pyridineethanol as an adhesion enhancer in the amount listed in Table 1, and a surfactant BYK-310 (manufactured by BYK-Chemie) in the amount listed in Table 1 were dissolved in propylene glycol monomethyl ether acetate to a solids concentration of 24% by mass to obtain positive-type photosensitive resin compositions for each of the Examples and Comparative Examples. Using the resulting positive-type photosensitive resin compositions, sensitivity, cross-sectional shape, and resolution were evaluated according to the following methods. The evaluation results are reported in Table 1.

[0151] Sensitivity

[0152] A sample of the positive photosensitive resin composition was applied onto an 8-inch Si wafer using a spin coater to form a coating film, which was then dried at 110° C. for 90 seconds using a direct hot plate (DHP) to form a resist film having a thickness of 1.5 μm.

[0153] Next, exposure was performed using FPA-5510iv (trade name, manufactured by Canon, NA=0.12) via a test pattern mask (reticle) on which a mask pattern was drawn for realizing a 1.3 μm line and space pattern.

[0154] The exposed resist film was brought into contact with a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 65 seconds at 23° C. for development. The obtained resist pattern was washed with water for 30 seconds and spin-dried.

[0155] The shape of the obtained resist pattern was observed by SEM (scanning electron microscope) photography, and the exposure dose that gave a pattern size of 1.3 μm was confirmed. Based on the exposure dose that gave a pattern size of 1.30 μm, the sensitivity was evaluated according to the following criteria.

[0156] ◎: The exposure dose for a pattern size of 1.3 μm is less than 45 mJ / cm 2 .

[0157] ○: The exposure dose for a pattern size of 1.3 μm is 45 mJ / cm 2 Above and less than 55mJ / cm 2 .

[0158] ×: The exposure dose for a pattern size of 1.3 μm was 55 mJ / cm 2 above.

[0159] <Cross-sectional shape>

[0160] Using SEM photographs, the cross-sectional shapes of the 1.3-μm line and space patterns obtained in the above sensitivity evaluation were observed, and the cross-sectional shapes were evaluated according to the following criteria.

[0161] ◎: Rectangular shape

[0162] 〇: T-top shape where the width near the surface of the resist pattern on the side opposite to the substrate is thicker than the width near the center in the height direction of the resist pattern

[0163] ×: Without a head (Japanese: 頭付き無し) (pattern shape with a cross-sectional shape close to a triangle)

[0164] <Resolution>

[0165] Using the same method as the above sensitivity evaluation, masks for realizing 1.3-μm line and space patterns, masks for realizing 1.2-μm line and space patterns, and masks for realizing 1.1-μm line and space patterns were used, and exposure was performed with an exposure amount capable of reproducing the 1.3-μm line and space patterns in terms of size to form line and space patterns. The obtained line and space patterns were observed by SEM photographs, and resolution was evaluated according to the following criteria. It should be noted that in the case where the evaluation of the cross-sectional shape is ×, since it is difficult to evaluate, the resolution evaluation was not performed.

[0166] 1.3: Can resolve 1.3-μm line and space patterns, but cannot resolve 1.2-μm line and space patterns.

[0167] 1.2: Can resolve 1.2-μm line and space patterns, but cannot resolve 1.1-μm line and space patterns.

[0168]

[0169] As can be seen from Table 1, the positive photosensitive resin composition containing a Novolac resin (A), a compound containing a quinonediazide group (B), a sensitizer (C) satisfying specified requirements, and a resin (D) containing phenolic hydroxyl groups in a specified amount within a specified range has excellent sensitivity and can provide a patterned resist film with a good cross-sectional shape.

Claims

1. A positive photosensitive resin composition comprising a Novolac resin (A), a compound containing a quinonediazide group (B), a sensitizer (C), and a resin containing a phenolic hydroxyl group (D). The compound (B) containing a quinonediazide group comprises 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 formula (B1), R b1 are each independently an alkyl group having 1 to 5 carbon atoms, each D is independently a hydrogen atom or a 1,2-diazide naphthoquinone-5-sulfonyl group, at least one of the 2+m Ds is a 1,2-diazide naphthoquinone-5-sulfonyl group, and each l and m are independently 1 or 2. [Chemical Formula 2] In formula (B2), D is independently a hydrogen atom or a 1,2-diazide naphthoquinone-5-sulfonyl group, and at least one of the three Ds is a 1,2-diazide naphthoquinone-5-sulfonyl group. [Chemical Formula 3] In formula (B3), R b3 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R b4 each 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-diazide naphthoquinone-5-sulfonyl group, and at least one of the four Ds represents a 1,2-diazide naphthoquinone-5-sulfonyl group. The sensitizer (C) is a compound having a phenolic hydroxyl group and a molecular weight of 1000 or less. The resin (D) containing phenolic hydroxyl groups is a homopolymer of hydroxystyrene having a weight average molecular weight of 3,000 to 15,000. 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 relative to 100 parts by mass of the Novolac resin (A).

2. The positive photosensitive resin composition according to claim 1, wherein The content of the sensitizer (C) is 10 parts by mass or more and 30 parts by mass or less relative to 100 parts by mass of the Novolac resin (A).

3. A method for forming a patterned resist film, comprising the following steps: A step of applying the positive photosensitive resin composition according to claim 1 or 2 to a substrate to form a coating film; a step of exposing the coating film in a position-selective manner; and A step of developing the exposed coating film with a developer. 4 . A patterned resist film formed from the positive photosensitive resin composition according to claim 1 .

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