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

Abstract

To provide a positive type photosensitive resin composition with high sensitivity, with which a patterned resist film having an excellent cross-sectional shape can be formed, a forming method of the patterned resist film using the positive type photosensitive resin composition, and the patterned resist film composed of the positive type photosensitive resin composition.SOLUTION: A positive type photosensitive resin composition is made to contain a novolac resin (A), a quinonediazide group-containing compound (B), a sensitizer (C) being a compound having a phenolic hydroxy group with molecular weight of 1,000 or less, and a phenolic hydroxy group-containing resin (D) with an amount within a predetermined range which is a resin having weight average molecular weight of more than 1,000 other than the novolac resin (A).SELECTED DRAWING: None

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 technology]

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

[0003] A typical method for forming a resist pattern when forming wiring or terminals on a substrate is to form a photosensitive composition layer on the substrate using a dry film made of a negative photosensitive composition, and then expose and develop the photosensitive composition layer. However, when a negative photosensitive composition is used, there are problems such as insufficient resolution and difficulty in peeling the resist pattern from the substrate.

[0004] Therefore, one method for solving the above problems is to form a resist pattern using a positive-type photosensitive composition which has good resolution and is relatively easy to peel off from a substrate. Known positive-type photosensitive compositions that can be used to form metal wiring, terminals, and the like include photosensitive compositions that contain, for example, an alkali-soluble novolak resin such as a cresol novolak resin, a photosensitizer, and a benzotriazole-based compound (see Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2010-176012 A Summary of the Invention [Problem to be solved by the invention]

[0006] When forming fine wiring or terminals, it is required that the photosensitive composition can be used to form a resist pattern having a cross-sectional shape close to a rectangle, and that the photosensitive composition has high sensitivity. However, with the positive-type photosensitive composition as described in Patent Document 1, it is difficult to achieve both a good cross-sectional shape of the resist pattern and high sensitivity.

[0007] The present invention has been made in consideration of the above problems, and has an object to provide a highly sensitive positive photosensitive resin composition capable of forming a patterned resist film with a good cross-sectional shape, a method for forming a patterned resist film using the positive photosensitive resin composition, and a patterned resist film made of the positive photosensitive resin composition. [Means for solving the problem]

[0008] The present inventors have found that the above problems can be solved by incorporating into a positive-type photosensitive resin composition a novolak resin (A), a quinone diazide group-containing compound (B), a sensitizer (C) which is a compound having a phenolic hydroxyl group and a molecular weight of 1000 or less, and a phenolic hydroxyl group-containing resin (D) other than the novolak resin (A) which has a weight-average molecular weight of more than 1000 and is in a predetermined amount within a specified range, and have thus completed the present invention. Specifically, the present invention provides the following.

[0009] A first aspect of the present invention includes a novolak resin (A), a quinone diazide group-containing compound (B), a sensitizer (C), and a phenolic hydroxyl group-containing resin (D), the sensitizer (C) is a compound having a molecular weight of 1000 or less and having a phenolic hydroxyl group, the phenolic hydroxyl group-containing resin (D) is a resin other than the novolak resin (A) having a weight average molecular weight of more than 1000; The content of the phenolic hydroxyl group-containing resin (D) is from 0.5 to 10 parts by mass based on 100 parts by mass of the novolak resin (A) in the positive photosensitive resin composition.

[0010] A second aspect of the present invention is a method for producing a photosensitive resin composition for a photosensitive resin film, comprising the steps of: applying the positive-type photosensitive resin composition according to the first aspect to a substrate to form a coating film; A step of position-selectively exposing the coating film; developing the exposed coating film with a developer; The present invention relates to a method for forming a patterned resist film, comprising the steps of:

[0011] A third aspect of the present invention is a patterned resist film comprising the positive photosensitive resin composition according to the first aspect. Effect of the Invention

[0012] According to the present invention, it is possible to provide a highly sensitive positive photosensitive resin composition capable of forming a patterned resist film with a good cross-sectional shape, a method for forming a patterned resist film using the positive photosensitive resin composition, and a patterned resist film made of the positive photosensitive resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] <Positive-type photosensitive resin composition> The positive-type photosensitive resin composition contains a novolak resin (A), a quinone diazide group-containing compound (B), a sensitizer (C), and a phenolic hydroxyl group-containing resin (D). The sensitizer (C) is a compound having a molecular weight of 1,000 or less and containing a phenolic hydroxyl group. The phenolic hydroxyl group-containing resin (D) is a resin having a weight average molecular weight of more than 1,000 other than the novolak resin (A). The content of the phenolic hydroxyl group-containing resin (D) is from 0.5 to 10 parts by mass based on 100 parts by mass of the novolak resin (A). The positive photosensitive resin composition having the above-mentioned structure can achieve both a good cross-sectional shape for the patterned resist film and high sensitivity. Hereinafter, essential and optional components contained in the positive photosensitive resin composition will be described.

[0014] <Novolac resin (A)> As the novolac resin (A), various novolac resins that have been conventionally blended in positive-type photosensitive resin compositions can be used. As the novolac resin (A), those obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenols") and an aldehyde in the presence of an acid catalyst are preferred.

[0015] Phenols Examples of 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 p-tert- Examples of such phenols include alkylphenols such as butylphenol, trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol, polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglucinol, alkyl polyhydric phenols such as alkylresorcin, alkylcatechol, and alkylhydroquinone (each alkyl group has 1 to 4 carbon atoms), α-naphthol, β-naphthol, hydroxydiphenyl, and bisphenol A. These phenols may be used alone or in combination of two or more.

[0016] Among these phenols, m-cresol and p-cresol are preferred, and it is more preferred to use m-cresol and p-cresol in combination. In this case, by adjusting the blending ratio of the two, various properties such as the sensitivity as a positive photosensitive resin composition and the heat resistance of the resist film formed can be adjusted. The blending ratio of m-cresol and p-cresol is not particularly limited, but the mass ratio of m-cresol / p-cresol is preferably 3 / 7 or more and 8 / 2 or less. When the ratio of m-cresol is 3 / 7 or more, the sensitivity as a positive photosensitive resin composition can be improved, and when it is 8 / 2 or less, the heat resistance of the resist film formed using the photosensitive resin composition can be improved.

[0017] ·Aldehydes Examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, etc. These aldehydes may be used alone or in combination of two or more kinds.

[0018] 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, diethylsulfuric acid, and paratoluenesulfonic acid, and metal salts such as zinc acetate, etc. These acid catalysts may be used alone or in combination of two or more.

[0019] ·Molecular weight The polystyrene-equivalent weight average molecular weight (Mw; hereinafter, simply referred to as "weight average molecular weight") of the novolak resin (A) is, from the viewpoints of developability, resolution, and the like of the positive-type photosensitive resin composition, preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 3,000 or more, and 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.

[0020] The dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the novolak 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 this specification, the weight average molecular weight Mw and the number average molecular weight Mn can be defined as relative values ​​calculated in terms of polystyrene in GPC (gel permeation chromatography) measurement. When multiple types of novolak resins (A) are used, a GPC (gel permeation chromatography) measurement is carried out on a combination of these multiple types of novolak resins (A), and the dispersity can be determined from the obtained chart.

[0021] As the novolak resin (A), at least two types of resins having different weight average molecular weights in terms of polystyrene can be used in combination. By using a combination of resins having different weight average molecular weights, it is possible to impart excellent properties in many aspects, such as developability, resolution, and film-forming property, to the positive photosensitive resin composition. As the novolak resin (A), the combination of resins having different weight average molecular weights is not particularly limited, but a combination of a low weight average molecular weight resin having a weight average molecular weight of 1000 or more and 10,000 or less and a high weight average molecular weight resin having a weight average molecular weight of 5000 or more and 50,000 or less is preferred, a combination of a low weight average molecular weight resin having a weight average molecular weight of 2000 or more and 8000 or less and a high weight average molecular weight resin having a weight average molecular weight of 8000 or more and 40,000 or less is more preferred, and a combination of a low weight average molecular weight resin having a weight average molecular weight of 3000 or more and 7000 or less and a high weight average molecular weight resin having a weight average molecular weight of 10,000 or more and 20,000 or less is even more preferred.

[0022] When resins having different weight-average molecular weights are used in combination as the novolac resin (A), the respective contents are not particularly limited, but the content of the resin having a lower weight-average molecular weight in the total amount of the novolac resin (A) is preferably 5 mass% or more, more preferably 10 mass% or more, and even more preferably 15 mass% or more, while it is preferably 50 mass% or less, and more preferably 40 mass% or less.

[0023] The mass ratio of the novolak resin (A) to the total solid content of the positive-type photosensitive resin composition is not particularly limited, as long as the positive-type photosensitive resin composition contains desired amounts of the quinone diazide group-containing compound (B), the sensitizer (C), and the phenolic hydroxyl group-containing resin (D). The mass ratio of the novolak 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 even more preferably 50 mass % or more and 70 mass % or less.

[0024] <Quinonediazide group-containing compound (B)> The positive photosensitive resin composition contains a quinone diazide group-containing compound (B). The quinone diazide group-containing compound (B) can be appropriately selected from compounds having a quinone diazide group that have been conventionally blended in various positive photosensitive resin compositions.

[0025] Specific preferred examples of the quinone diazide group-containing compound (B) 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, and 2,2',3,4,4'-pentahydroxybenzophenone. polyhydroxybenzophenones such as 2,2',3,4,5-pentahydroxybenzophenone, 2,3',4,4',5',6-hexahydroxybenzophenone, and 2,3,3', and 4,4',5'-hexahydroxybenzophenone; bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(2, Bis[(poly)hydroxyphenyl]alkanes such as 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-hydroxyphenyl tris(hydroxyphenyl)methanes or methyl-substituted derivatives thereof, 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-cyclo Bis(3-cyclohexyl-2-hydroxyphenyl)-3-hydroxyphenylmethane, Bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-4-hydroxyphenylmethane, Bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-3-hydroxyphenylmethane, Bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, Bis(3- Examples of the hydroxyphenyl group-containing compounds include bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methanes or methyl-substituted compounds thereof, such as bis(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, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine, and 4,4'-diaminobenzophenone; and complete ester compounds, partial ester compounds, amidated products, or partial amidated products of pyrogallol-acetone resin and a quinone diazide group-containing sulfonic acid. These quinonediazide group-containing compounds (B) may be used alone or in combination of two or more kinds.

[0026] The quinone diazide group-containing sulfonic acid used as the quinone diazide group-containing compound (B) is not particularly limited, but examples thereof include naphthoquinone diazide sulfonic acids such as naphthoquinone-1,2-diazide-5-sulfonic acid and naphthoquinone-1,2-diazide-4-sulfonic acid; orthoanthraquinone diazide sulfonic acid, and naphthoquinone diazide sulfonic acid is preferred. The quinone diazide group-containing sulfonic acid, preferably the above ester compound of naphthoquinone diazide sulfonic acid, dissolves well in a solvent that is usually used when using a positive composition as a solution, and has good compatibility with the novolac resin (A). When these compounds are blended as the quinone diazide group-containing compound (B) in a positive photosensitive resin composition, a high-sensitivity positive photosensitive resin composition is easily obtained.

[0027] The method for producing the ester compound as the quinone diazide group-containing compound (B) is not particularly limited, and examples thereof include a method in which a quinone diazide group-containing sulfonic acid is added as a sulfonyl chloride such as naphthoquinone-1,2-diazide-sulfonyl chloride, and condensed in a solvent such as dioxane in the presence of an alkali such as triethanolamine, an alkali carbonate, or an alkali hydrogen carbonate to perform complete or partial esterification.

[0028] In addition, it is also preferable that the positive photosensitive resin composition contains a combination of 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 group-containing compound, in that the positive photosensitive resin composition has good sensitivity and resolution and that a patterned resist film having a good shape can be easily formed using the positive photosensitive resin composition.

[0029] [ka] (In formula (B1), R b1are each independently an alkyl group having 1 to 5 carbon atoms, each D is independently a hydrogen atom or a 1,2-naphthoquinone diazide-5-sulfonyl group, at least one of the 2+m D's is a 1,2-naphthoquinone diazide-5-sulfonyl group, and each l and m is independently 1 or 2.

[0030] [ka] (In formula (B2), each D is independently a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of the three Ds is a 1,2-naphthoquinonediazide-5-sulfonyl group.) and a compound represented by the following formula (B3):

[0031] [ka] (In formula (B3), R b3 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R b4 are each independently a hydrogen atom, a halogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or a cycloalkyl group having from 3 to 6 carbon atoms, and each D is independently a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of the four Ds is a 1,2-naphthoquinonediazide-5-sulfonyl group.

[0032] In formula (B1), R b1 are each independently an alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms may be linear or branched. Specific preferred examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, and a neopentyl group. R b1As the alkyl group, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.

[0033] In order to easily control the solubility in a developer and the sensitivity of the positive-type photosensitive resin composition within appropriate ranges, the average proportion (average esterification rate) of D that is a 1,2-naphthoquinonediazide-5-sulfonyl group in the quinonediazide ester represented by formula (B1) is preferably 40% or more and 60% or less, and more preferably 50% or more and 55% or less.

[0034] In order to easily adjust the solubility in a developer and the sensitivity of the positive-type photosensitive resin composition to within appropriate ranges, the average proportion (average esterification rate) of D which is a 1,2-naphthoquinonediazide-5-sulfonyl group in the quinonediazide ester represented by formula (B2) is preferably 65% ​​or more and 85% or less, and more preferably 70% or more and 75% or less.

[0035] In formula (B3), R b3 are each independently 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. Specific preferred examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group. R b3 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom group.

[0036] In formula (B3), R b4 are each independently a hydrogen atom, a halogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or a cycloalkyl group having from 3 to 6 carbon atoms. An alkyl group having 1 to 6 carbon atoms is R b3 The alkyl group is the same as the alkyl group represented by the formula (I). Specific examples of alkoxy groups having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, an isopentyloxy group, a neopentyloxy group, and an n-hexyloxy group. Specific examples of the cycloalkyl group having 3 to 6 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Of these, the cyclohexyl group is preferred.

[0037] 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) to the sum (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, more preferably 40 / 60 or more and 60 / 40 or less.

[0038] The content of the quinone diazide group-containing compound (B) is preferably within the following range in terms 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, relative to 100 parts by mass of the novolak resin (A). The upper limit 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 novolak resin (A).

[0039] <Sensitizer (C)> The positive-type photosensitive resin composition contains a sensitizer (C). The sensitizer (C) is a compound having a molecular weight of 1,000 or less and containing a phenolic hydroxyl group. The positive-type photosensitive resin composition contains a combination of the novolak resin (A), the quinone diazide group-containing compound (B), the sensitizer (C), and the phenolic hydroxyl group-containing resin (D), so that it is easy to achieve both a good cross-sectional shape of the patterned resist film and high sensitivity.

[0040] Suitable examples of the compound that can be used as the sensitizer (C) include various phenolic hydroxyl group-containing compounds as explained for the quinonediazide group-containing compound (B). 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, 2 , 2',3,4,5-pentahydroxybenzophenone, 2,3',4,4',5',6-hexahydroxybenzophenone, 2,3,3', and 4,4',5'-hexahydroxybenzophenone; polyhydroxybenzophenones 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 bis[(poly)hydroxyphenyl]alkanes such as 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-hydroxyphenyl tris(hydroxyphenyl)methanes or methyl-substituted compounds thereof, 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 Examples of the hydroxyphenylmethane include bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methanes or methyl-substituted bis(cyclohexylhydroxyphenyl)methane, 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; and compounds having a hydroxyl group such as phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, and gallic acid.

[0041] The content of the sensitizer (C) is not particularly limited as long as it does not impair the object of the present invention. Since it is easy to obtain the desired effects on the cross-sectional shape and sensitivity of the resist film, 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 even more preferably 15 parts by mass or more and 20 parts by mass or more, based on 100 parts by mass of the novolak resin (A).

[0042] <Phenol-containing hydroxyl group resin (D)> The positive-type 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 of more than 1,000 other than the novolak resin (A). When the positive-type photosensitive resin composition contains the novolak resin (A) and the sensitizer (C), as well as the phenolic hydroxyl group-containing resin (D) in a specified amount described below, the positive-type photosensitive resin composition exhibits appropriate solubility in a developer, and it is easy to achieve both a good cross-sectional shape of the patterned resist film and high sensitivity without impairing the strength, etc., of the resist film.

[0043] The content of the phenolic hydroxyl group-containing resin (D) is from 0.5 to 10 parts by mass, more preferably from 1 to 9 parts by mass, and even more preferably from 2 to 8 parts by mass, per 100 parts by mass of the novolak resin (A).

[0044] The phenolic hydroxyl group-containing resin (D) is not particularly limited as long as it is a resin other than the novolak resin (A) and has a weight average molecular weight of more than 1000. Resins preferable as 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)acrylic acid ester having a hydroxyphenyl group which may have a substituent.

[0045] When the phenolic hydroxyl group-containing resin (D) is a resin containing structural units derived from hydroxystyrene which may have a substituent, and / or structural units derived from a (meth)acrylic acid ester having a hydroxyphenyl group which may have a substituent, the amount of structural units having a phenolic hydroxyl group in the resin is preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 90 mol % or more, and most preferably 100 mol % based on the total structural units.

[0046] As the constitutional unit derived from hydroxystyrene which may have a substituent, a constitutional unit represented by the following formula (D1) is preferred. [ka] (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 may be the same or different.)

[0047] An example of an alkyl group having from 1 to 6 carbon atoms is a linear or branched alkyl group having from 1 to 6 carbon atoms. Examples of linear or branched alkyl groups 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 from 1 to 6 carbon atoms is, for example, a linear or branched alkoxy group having from 1 to 6 carbon atoms. Examples of the linear or branched alkyl group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a tert-butyloxy group, an n-pentyloxy group, an isopentyloxy group, and a neopentyloxy group. Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0048] Specific preferred examples of monomers that provide 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, etc. 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.

[0049] As the structural unit derived from a (meth)acrylic acid ester having a hydroxyphenyl group which may have a substituent, a structural unit represented by the following formula (D2) is preferred. [ka] (In formula (D2), R d2 and n are the same as those in formula (D1). d3 is a hydrogen atom or a methyl group. d4 is a single bond or an alkylene group having 1 to 4 carbon atoms.

[0050] R d4 Examples of the alkylene group as 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, a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group are preferred, and a methylene group and an ethylene group are more preferred.

[0051] Specific preferred examples of monomers that provide the structural unit represented by formula (D2) include phenolic hydroxyl group-containing acrylates 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, as well as phenolic hydroxyl group-containing methacrylates 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. Of 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.

[0052] 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. Examples of such other monomers include known radical polymerizable compounds and anion 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 carboxy group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic 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. hydroxyalkyl acrylates; aryl (meth)acrylate esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid 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 diolefins 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; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.

[0053] As the phenolic hydroxyl group-containing resin (D) described above, 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 which may have a substituent is more preferred, a homopolymer of hydroxystyrene is even more preferred, and a homopolymer of 4-hydroxystyrene is particularly preferred, because the desired effects can be easily obtained by using a phenolic hydroxyl group-containing resin.

[0054] As described above, the weight average molecular weight of the phenolic hydroxyl group-containing resin (D) is not particularly limited as long as it is more than 1000. The weight average molecular weight of the phenolic hydroxyl group-containing resin (D) is preferably 3000 to 15000, more preferably 4000 to 13000, and even more preferably 5000 to 10000, since a positive-type photosensitive resin composition having particularly suitable solubility in a developer can be easily obtained.

[0055] <Other ingredients> The positive composition may contain various additives such as colorants, sensitizers, adhesion improvers, surfactants, plasticizers, etc., within the scope of not impairing the object of the present invention.

[0056] Sensitizer The sensitizer is not particularly limited and can be selected from sensitizers that are commonly used in positive-type photosensitive resin compositions. Examples of the sensitizer include compounds having a phenolic hydroxyl group and a molecular weight of 1000 or less.

[0057] Adhesion improver The adhesion improver can be appropriately selected from materials capable of improving the adhesion of the patterned resist film to 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.

[0058] Surfactants The positive photosensitive resin composition may contain a surfactant in order to improve the coating properties, defoaming properties, leveling properties, and the like. As the surfactant, for example, commercially available silicone-based or fluorine-based surfactants under the names BM-1000, BM-1100 (manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, Megafac F183 (manufactured by Dainippon Ink & Chemicals), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (manufactured by Sumitomo 3M), Surflon S-112, 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) can be used.

[0059] The content of the surfactant is preferably 0.05 parts by mass or more and 5 parts by mass or less based on 100 parts by mass of the novolak resin (A).

[0060] <Solvent> The positive photosensitive resin composition is preferably used in the form of a solution by dissolving the above-mentioned components in a suitable solvent. Examples of such a solvent 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 monomethyl ether acetate, propylene glycol monoethyl ether acetate, and Examples of the solvent include propylene glycol alkyl ether acetates such as propylene glycol monopropyl 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-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 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.

[0061] 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% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 30% by mass or less.

[0062] <Method for preparing positive-type photosensitive resin composition> The positive-type photosensitive resin composition can be prepared by mixing the above-mentioned components in a predetermined ratio, and then mixing and stirring them in a conventional manner. If necessary, the mixture may be filtered using a mesh or membrane filter.

[0063] <Method for forming a patterned resist film> The patterned resist film is formed by a process comprising the steps of: applying the positive photosensitive resin composition to a substrate to form a coating film; A step of position-selectively exposing the coating film; developing the exposed coating film with a developer; The composite may be formed by a method comprising:

[0064] The positive photosensitive resin composition is applied to a substrate using a spinner, a roll coater, a spray coater, a slit coater, or the like. The coating device is not limited to these. Usually, the coating film is dried by a method such as heating. The drying method may be, for example, (1) a method of drying the coating film on a hot plate at a temperature of 80° C. to 120° C. for 60 to 120 seconds, (2) a method of leaving the coating film at room temperature for several hours to several days, or (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 dried as necessary is not particularly limited, but is preferably about 1.0 μm to 5.0 μm.

[0065] The type of substrate is not particularly limited. The positive photosensitive resin composition described above has excellent sensitivity and is therefore easily applied to a substrate with a large area. For this reason, suitable substrates include substrates for displays such as liquid crystal displays and organic electroluminescence displays. Examples of such substrates for displays include glass plates that are provided with wiring such as transparent conductive circuits and, if necessary, are provided with a black matrix, a color filter, a polarizing plate, and the like.

[0066] Next, the coating film is exposed to light through a mask having a predetermined pattern corresponding to the pattern shape. The exposure is carried out by irradiating it with active energy rays such as ultraviolet light and excimer laser light. Examples of the light source for the active energy rays include a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high 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, but is, for example, 30 to 2000 mJ / cm. 2 It's fine as long as it's to a certain extent.

[0067] The exposed coating film is then developed with a developer to form a patterned resist film. Examples of the developer include an aqueous solution of an organic alkali such as an aqueous solution of tetramethylammonium hydroxide (TMAH), or an aqueous solution of an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium metasilicate, or sodium phosphate. After development, the surface of the patterned resist film may be rinsed with water or an organic solvent that does not excessively dissolve the resist film, etc. Furthermore, the patterned resist film may be baked as necessary.

[0068] In this manner, a patterned resist film made of the positive photosensitive resin composition is formed. Such a resist film may be used as a protective film or an insulating film, a mask pattern for etching, or a mold for plating. EXAMPLES

[0069] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0070] [Examples 1 to 10 and Comparative Examples 1 to 6] In the examples and comparative examples, a cresol novolak resin (weight average molecular weight 6000) in which the mass ratio of m-cresol / p-cresol was 36 / 64 was used as the novolak resin (A) (component (A)).

[0071] In the examples and comparative examples, the following BI, B-II, and B-III were used as the quinone diazide group-containing compound (B) (component (B)). BI corresponds to the compound represented by the above formula (B1). B-II corresponds to the compound represented by the above formula (B2). B-III corresponds to the compound represented by the above formula (B3). The average introduction rate of the quinone diazide group in each compound (meaning how many moles of the substituent OD are substituted with the quinone diazide group on average) is 2.1 moles for BI, 1.7 moles for B-II, and 2.5 moles for B-III. [ka]

[0072] In the examples and comparative examples, the following CI and C-II were used as the sensitizer (C) (component (C)). CI: A compound represented by the following formula: C-II: Compound B-III in which all Ds are hydrogen atoms [ka]

[0073] In the examples and comparative examples, the following DI and D-II were used as the phenolic hydroxyl group-containing resin (D) (component (D)). DI: Homopolymer of 4-hydroxystyrene (weight average molecular weight 8000) D-II: A copolymer of 75% by mass of 4-hydroxystyrene and 25% by mass of styrene (weight average molecular weight 2500)

[0074] 100 parts by mass of novolak resin (A), the type and amount of quinone diazide group-containing compound (B) shown in Table 1, the amount of sensitizer (C) shown in Table 1, the type and amount of phenolic hydroxyl group-containing resin (D) shown in Table 1, the amount of 2-pyridineethanol as an adhesion enhancer shown in Table 1, and the amount of surfactant BYK-310 (manufactured by BYK-Chemie) shown in Table 1 were dissolved in propylene glycol monomethyl ether acetate to a solid content concentration of 24 mass, to obtain positive photosensitive resin compositions of each Example and Comparative Example. Using the obtained positive photosensitive resin composition, the sensitivity, cross-sectional shape, and resolution were evaluated according to the following method. The evaluation results are shown in Table 1.

[0075] <Sensitivity> A sample of the positive photosensitive resin composition was applied onto an 8-inch Si wafer using a spinner to form a coating film. The coating film was dried on a direct hot plate (DHP) at 110°C for 90 seconds to form a resist film with a thickness of 1.5 μm. Next, exposure was performed using an FPA-5510iv (product name, manufactured by Canon, NA=0.12) through a test chart mask (reticle) on which a mask pattern for realizing a 1.3 μm line and space pattern was drawn. The exposed resist film was developed by contacting it with a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 65 seconds at 23° C. The resulting resist pattern was washed with water for 30 seconds and spin-dried. The shape of the obtained resist pattern was observed by SEM (scanning electron microscope) photograph to confirm the exposure dose at which the pattern dimension was 1.3 μm. Based on the exposure dose at which the pattern dimension was 1.30 μm, the sensitivity was evaluated according to the following criteria. ◎: The exposure dose for a pattern dimension of 1.3 μm is 45 mJ / cm 2 is less than. ◯: The exposure dose at which the pattern dimension is 1.3 μm is 45 mJ / cm 2 More than 55mJ / cm 2 is less than. ×: The exposure dose resulting in a pattern dimension of 1.3 μm is 55 mJ / cm 2That's all.

[0076] <Cross-sectional shape> The cross-sectional shape of the 1.3 μm line and space pattern obtained in the above sensitivity evaluation was observed on a SEM photograph, and the cross-sectional shape was evaluated according to the following criteria. ◎: Rectangular shape ○: The width of the resist pattern near the surface on the opposite side of the substrate is wider than the width near the center of the resist pattern in the height direction, a T-top shape ×: No head (cross-sectional shape is close to a triangle)

[0077] <Resolution> Using the same method as in the sensitivity evaluation, a mask for realizing a 1.3 μm line and space pattern, a mask for realizing a 1.2 μm line and space pattern, and a mask for realizing a 1.1 μm line and space pattern were used to perform exposure at an exposure amount that allows the 1.3 μm line and space pattern to be reproduced exactly to size, to form a line and space pattern. The resulting line and space pattern was observed using a SEM photograph, and the resolution was evaluated according to the following criteria. In addition, when the evaluation of the cross-sectional shape was ×, the resolution was not evaluated because it was difficult to evaluate. 1.3: Capable of resolving 1.3 μm line and space patterns, but cannot resolve 1.2 μm line and space patterns. 1.2: Capable of resolving 1.2 μm line and space patterns, but not 1.1 μm line and space patterns.

[0078] [Table 1]

[0079] According to Table 1, it is seen that a positive-type photosensitive resin composition containing a novolak resin (A), a quinone diazide group-containing compound (B), a sensitizer (C) satisfying predetermined requirements, and a phenolic hydroxyl group-containing resin (D) satisfying predetermined requirements and in an amount within a predetermined range, gives a patterned resist film having excellent sensitivity and a good cross-sectional shape.

Claims

1. A composition comprising a novolak resin (A), a quinone diazide group-containing compound (B), a sensitizer (C), and a phenolic hydroxyl group-containing resin (D), The quinone diazide group-containing compound (B) is represented by the following formula (B1): [Case 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-naphthoquinone diazide-5-sulfonyl group, at least one of the 2+m D's is a 1,2-naphthoquinone diazide-5-sulfonyl group, and each l and m is independently 1 or 2. and a compound represented by the following formula (B2): [Case 2] (In formula (B2), D's are each independently a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of the three D's is a 1,2-naphthoquinonediazide-5-sulfonyl group.) and a compound represented by the following formula (B3): [C3] (In formula (B3), R ｂ３ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ｂ４ are each independently a hydrogen atom, a halogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or a cycloalkyl group having from 3 to 6 carbon atoms, and each D is independently a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of the four Ds is a 1,2-naphthoquinonediazide-5-sulfonyl group. The compound represented by the formula: the sensitizer (C) is a compound having a phenolic hydroxyl group and a molecular weight of 1,000 or less, the phenolic hydroxyl group-containing resin (D) is a resin other than the novolak resin (A) having a weight average molecular weight of more than 1,000, The positive photosensitive resin composition has a content of the phenolic hydroxyl group-containing resin (D) of 0.5 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the novolak resin (A).

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

3. 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 3,000 or more and 15,000 or less.

5. The positive photosensitive resin composition according to any one of claims 1 to 4, wherein the content of the sensitizer (C) is 10 parts by mass or more and 30 parts by mass or less based on 100 parts by mass of the novolak resin (A).

6. A step of applying the positive photosensitive resin composition according to any one of claims 1 to 5 onto a substrate to form a coating film; A step of position-selectively exposing the coating film; developing the exposed coating film with a developer; A method for forming a patterned resist film, comprising:

7. A patterned resist film comprising the positive photosensitive resin composition according to any one of claims 1 to 5.

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