JP2021026229A - Positive type photosensitive resin composition, forming method of patterned resist film, and patterned resist film - Google Patents

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

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

As a method of forming wiring and terminals on a substrate, a method of etching a metal layer using a resist pattern as a mask pattern or a method of performing plating using a resist pattern as a mold pattern for plating is known. ..

As a method of forming a resist pattern when forming wirings and terminals on a substrate, a photosensitive composition layer is formed on the substrate using a dry film made of a negative type photosensitive composition, and the photosensitive composition layer is formed. A method of exposing and developing a material layer is common. However, when a negative type photosensitive composition is used, there are problems such as insufficient resolution and difficulty in peeling the resist pattern from the substrate.

Therefore, as a method for solving the above problems, there is a method of forming a resist pattern using a positive photosensitive composition having good resolution and relatively easy peeling from the substrate. ..
Examples of the positive photosensitive composition that can be used for forming wirings and terminals made of metal include photosensitive resins containing an alkali-soluble novolak resin such as cresol novolac resin, a photosensitizer, and a benzotriazole compound. The composition is known (see Patent Document 1).

JP-A-2010-176012

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, in the positive 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.

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

The present inventors have added a novolak resin (A), a quinonediazide group-containing compound (B), and a sensitizer (C) which is a compound having a phenolic hydroxyl group having a molecular weight of 1000 or less in a positive photosensitive resin composition. The present invention has been found that the above problems can be solved by containing a resin having a weight average molecular weight of more than 1000 other than the novolak resin (A) and containing a phenolic hydroxyl group-containing resin (D) in an amount within a predetermined range. Has been completed. Specifically, the present invention provides the following.

The first aspect of the present invention comprises a novolak resin (A), a quinonediazide group-containing compound (B), a sensitizer (C), and a phenolic hydroxyl group-containing resin (D).
The sensitizer (C) is a compound having a phenolic hydroxyl group having a molecular weight of 1000 or less.
The phenolic hydroxyl group-containing resin (D) is a resin having a weight average molecular weight of more than 1000 other than the novolak resin (A).
This is a positive photosensitive resin composition in which the content of the phenolic hydroxyl group-containing resin (D) is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the novolak resin (A).

A second aspect of the present invention includes a step of applying the positive photosensitive resin composition according to the first aspect to a substrate to form a coating film.
The process of regioselectively exposing the coating film and
The process of developing the exposed coating film with a developer and
It is a method of forming a patterned resist film including.

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

According to the present invention, a patterned resist film having a good cross-sectional shape can be formed, and a highly sensitive positive photosensitive resin composition and a patterned resist film using the positive photosensitive resin composition are formed. A method and a patterned resist film made of the above-mentioned positive photosensitive resin composition can be provided.

≪Positive type photosensitive resin composition≫
The positive photosensitive resin composition contains a novolak resin (A), a quinonediazide group-containing compound (B), a sensitizer (C), and a phenolic hydroxyl group-containing resin (D).
The sensitizer (C) is a compound having a phenolic hydroxyl group having a molecular weight of 1000 or less.
The phenolic hydroxyl group-containing resin (D) is a resin having a weight average molecular weight of more than 1000 other than the novolak resin (A).
The content of the phenolic hydroxyl group-containing resin (D) is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the novolak resin (A).
The positive photosensitive resin composition having the above structure can achieve both a good cross-sectional shape of the patterned resist film and high sensitivity.
Hereinafter, essential or arbitrary components contained in the positive photosensitive resin composition will be described.

<Novolak resin (A)>
As the novolak resin (A), various novolak resins conventionally blended in the positive photosensitive resin composition can be used. The novolak resin (A) is preferably obtained by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenols") and aldehydes under an acid catalyst.

-Phenols Examples of phenols include phenols; cresols such as o-cresol, m-cresol, p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-. Xylenols such as xylenol, 3,4-xylenol, 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, p-ethylphenol; 2-isopropylphenol, 3-isopropylphenol, 4- Alkylphenols such as isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; Polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and fluoroglycinol; alkyl polyhydric phenols such as alkylresorcin, alkylcatechol, and alkylhydroquinone (all alkyl groups have 1 or more carbon atoms and 4). ); Α-naphthol; β-naphthol; hydroxydiphenyl; and bisphenol A and the like. These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination. In this case, by adjusting the blending ratio of both, it is possible to adjust various characteristics such as the sensitivity of the positive photosensitive resin composition and the heat resistance of the resist film to be formed. 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, it is formed by using the photosensitive resin composition. The heat resistance of the resist film can be improved.

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

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

-Molecular weight The polystyrene-equivalent weight average molecular weight (Mw; hereinafter, also simply referred to as "weight average molecular weight") of the novolak resin (A) is determined from the viewpoint of developability, resolution, etc. of the positive photosensitive resin composition. 1000 or more is preferable, 2000 or more is more preferable, 3000 or more is further preferable, 50,000 or less is preferable, 40,000 or less is more preferable, 30,000 or less is further preferable, and 20,000 or less is even more preferable.

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. preferable.
In this specification, the weight average molecular weight Mw and the number average molecular weight Mn can be defined as polystyrene-equivalent relative values in GPC (gel permeation chromatography) measurement.
When a plurality of types of novolak resin (A) are used, GPC (gel permeation chromatography) measurement may be performed with the plurality of types of novolak resin (A) combined, and the degree of dispersion may be determined from the obtained chart. ..

As the novolak resin (A), at least two types having different polystyrene-equivalent weight average molecular weights can be used in combination. By using a combination of large and small ones having different weight average molecular weights, it is possible to impart multifaceted excellent properties such as developability, resolution, and film forming property to the positive photosensitive resin composition.
The combination of the novolak resin (A) and the resins having different weight average molecular weights is not particularly limited, but the resin having a weight average molecular weight of 1000 or more and 10,000 or less on the low weight average molecular weight side and the weight average molecular weight of 5000 or more and 50,000 or less. The combination with the resin on the high weight average molecular weight side is preferable, and the resin on the low weight average molecular weight side having a weight average molecular weight of 2000 or more and 8000 or less and the resin on the high weight average molecular weight side having a weight average molecular weight of 8000 or more and 40,000 or less are preferable. The combination with the resin is more preferable, and the combination of the resin on the low weight average molecular weight side having a weight average molecular weight of 3000 or more and 7,000 or less and the resin on the high weight average molecular weight side having a weight average molecular weight of 10,000 or more and 20000 or less is further preferable. ..

When resins having different weight average molecular weights are used in combination as the novolak resin (A), the content of each is not particularly limited, but the content of the resin on the low weight average molecular weight side in the total amount of the novolak resin (A) is 5. It is preferably mass% or more, more preferably 10% by mass or more, further preferably 15% by mass or more, while preferably 50% by mass or less, more preferably 40% by mass or less.

The ratio of the mass of the novolak resin (A) to the total solid content of the positive photosensitive resin composition was such that the positive photosensitive resin composition contained a desired amount of the quinonediazide group-containing compound (B) and a sensitizer (C). ) And the phenolic hydroxyl group-containing resin (D) are not particularly limited.
The ratio of the mass of the novolak 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 more preferably 50% by mass or more. 70% by mass or less is more preferable.

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

Suitable specific 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, 2,2', 3,4,4'-pentahydroxybenzophenone, 2,2', 3,4,5-pentahydroxybenzophenone, 2,3', Polyhydroxybenzophenones such as 4,4', 5', 6-hexahydroxybenzophenone, 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- (2,3,4-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 and other bis [(poly) hydroxyphenyl] alkanes; tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenyl Methan, 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 and other tris (hydroxyphenyl) methanes or methyl substituents thereof; bis (3-cyclohexyl-4-hydroxyphenone) Nyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl) -4-Hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2) -Methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -4-hydroxyphenylmethane , Bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl) -2-Hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -2-hydroxy Bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes such as phenylmethane and bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane or methyl substituents thereof; phenol, p-methoxy Hydroxy groups or amino groups such as phenol, dimethylphenol, hydroquinone, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine, and 4,4'-diaminobenzophenone. Examples thereof include a complete ester compound of a pyrogallol-acetone resin and the like and a quinonediazide group-containing sulfonic acid, a partial ester compound, an amidate, a partial amidate, and the like. These quinonediazide group-containing compounds (B) may be used alone or in combination of two or more.

The quinone diazide group-containing sulfonic acid used as the quinone diazide group-containing compound (B) is not particularly limited, and is, for example, naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-. Naftquinone diazido sulfonic acid such as sulfonic acid; orthoanthraquinone diazido sulfonic acid and the like can be mentioned, and naphthoquinone diazido sulfonic acid is preferable. The above ester compound of quinonediazide group-containing sulfonic acid, preferably naphthoquinonediazide sulfonic acid, dissolves well in a solvent usually used when a positive composition is used as a solution, and has good compatibility with novolak resin (A). Is. When these compounds are blended with the positive photosensitive resin composition as the quinonediazide group-containing compound (B), it is easy to obtain a highly sensitive positive photosensitive resin composition.

The method for producing the above ester compound as the quinonediazide group-containing compound (B) is not particularly limited, and for example, a quinonediazide group-containing sulfonic acid is added as a sulfonyl chloride such as naphthoquinone-1,2-diazide-sulfonyl chloride. Then, in a solvent such as dioxane, a method of condensing in the presence of an alkali such as triethanolamine, alkali carbonate, alkali hydrogencarbonate and the like to complete esterification or partial esterification can be mentioned.

Further, the positive photosensitive resin composition is represented as a quinonediazide group-containing compound by 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). The combination with the compound also contains the positive sensitivity and resolution of the positive photosensitive resin composition, and a patterned resist film having a good shape using the positive photosensitive resin composition. It is preferable because it is easy to form.

（式（Ｂ１）中、Ｒ^ｂ１は、それぞれ独立に炭素原子数１以上５以下のアルキル基であり、Ｄは、それぞれ独立に、水素原子、又は１，２−ナフトキノンジアジド−５−スルホニル基であり、２＋ｍ個のＤのうちの少なくとも１つが１，２−ナフトキノンジアジド−５−スルホニル基であり、ｌ、及びｍは、それぞれ独立に１又は２である。）

(In the formula (B1), R ^b1 is an alkyl group having 1 or more and 5 or less carbon atoms independently, and D is independently a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group. Yes, at least one of the 2 + m Ds is a 1,2-naphthoquinonediazide-5-sulfonyl group, and l and m are independently 1 or 2, respectively.)

（式（Ｂ２）中、Ｄは、それぞれ独立に、水素原子、又は１，２−ナフトキノンジアジド−５−スルホニル基であり、３個のＤのうちの少なくとも１つが１，２−ナフトキノンジアジド−５−スルホニル基である。）
で表される化合物と、下記式（Ｂ３）：

(In formula (B2), D is a hydrogen atom or 1,2-naphthoquinonediazide-5-sulfonyl group, respectively, and at least one of the three Ds is 1,2-naphthoquinonediazide-5. -Sulfonyl group.)
The compound represented by and the following formula (B3):

（式（Ｂ３）中、Ｒ^ｂ３は、それぞれ独立に、水素原子、又は炭素原子数１以上６以下のアルキル基であり、Ｒ^ｂ４は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１以上６以下のアルキル基、炭素原子数１以上６以下のアルコキシ基、又は炭素原子数３以上６以下のシクロアルキル基であり、Ｄは、それぞれ独立に、水素原子、又は１，２−ナフトキノンジアジド−５−スルホニル基であり、４個のＤのうちの少なくとも１つが１，２−ナフトキノンジアジド−５−スルホニル基である。）

(In the formula (B3), R ^b3 is independently a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms, and R ^b4 is independently a hydrogen atom, a halogen atom, and 1 carbon atom. It is an alkyl group having 6 or less, an alkoxy group having 1 or more and 6 or less carbon atoms, or a cycloalkyl group having 3 or more and 6 or less carbon atoms, and D is independently a hydrogen atom or 1,2-naphthoquinonediazide. It is a -5-sulfonyl group, and at least one of the four Ds is a 1,2-naphthoquinonediazide-5-sulfonyl group.)

In the formula (B1), R ^b1 is an alkyl group having 1 to 5 carbon atoms independently. The alkyl group having 1 or more and 5 or less carbon atoms may be linear or branched. Preferable specific examples of the alkyl group having 1 or more and 5 or less 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 and a tert-butyl group. Examples thereof include an n-pentyl group, an isopentyl group, and a neopentyl group.
As R ^b1 , a methyl group and an ethyl group are preferable, and a methyl group is more preferable.

D is 1,2-naphthoquinonediazide-5 in the quinonediazide esterified product represented by the formula (B1) from the viewpoint that the solubility of the positive photosensitive resin composition in the developing solution and the sensitivity can be easily kept within an appropriate range. The average ratio of −sulfonyl groups (average esterification rate) is preferably 40% or more and 60% or less, and more preferably 50% or more and 55% or less.

D is 1,2-naphthoquinonediazide-5 in the quinonediazide esterified product represented by the formula (B2) from the viewpoint that the solubility of the positive photosensitive resin composition in the developing solution and the sensitivity can be easily kept within an appropriate range. The average ratio of −sulfonyl groups (average esterification rate) is preferably 65% or more and 85% or less, and more preferably 70% or more and 75% or less.

In the formula (B3), R ^b3 is an alkyl group having a hydrogen atom and a carbon atom number of 1 or more and 6 or less, respectively. The alkyl group having 1 or more and 6 or less carbon atoms may be linear or branched. Preferable specific examples of the alkyl group having 1 or more and 6 or less 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 and a tert-butyl group. Examples thereof include n-pentyl group, isopentyl group, neopentyl group, n-hexyl and the like.
As R ^b3 , a hydrogen atom or a methyl group is preferable, and a hydrogen atom group is more preferable.

In the formula (B3), R ^b4 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 6 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or 3 or more and 6 or less carbon atoms. It is a cycloalkyl group of.
The alkyl group having 1 or more and 6 or less carbon atoms is the same as the alkyl group as ^{R b3.}
Specific examples of the alkoxy group having 1 or more and 6 or less 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, and a tert-butyloxy group. , N-pentyloxy group, isopentyloxy group, neopentyloxy group, n-hexyloxy and the like.
Specific examples of the cycloalkyl group having 3 or more and 6 or less carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Of these, a cyclohexyl group is preferable.

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

The content of the quinonediazide group-containing compound (B) is preferably in the following range from the viewpoint of the sensitivity of the positive photosensitive resin composition. Regarding the lower limit, 5 parts by mass or more is preferable, and 10 parts by mass or more is more preferable with respect to 100 parts by mass of the novolak resin (A). Regarding the upper limit, 100 parts by mass or less is preferable, 50 parts by mass or less is more preferable, and 30 parts by mass or less is further preferable with respect to 100 parts by mass of the novolak resin (A).

<Sensitizer (C)>
The positive photosensitive resin composition contains a sensitizer (C). The sensitizer (C) is a compound having a phenolic hydroxyl group having a molecular weight of 1000 or less.
The positive photosensitive resin composition contains a novolak resin (A), a quinonediazide group-containing compound (B), a sensitizer (C), and a phenolic hydroxyl group-containing resin (D) in combination to form a pattern. It is easy to achieve both a good cross-sectional shape of the plasticized resist film and high sensitivity.

Preferable examples of the compound that can be used as the sensitizer (C) include various phenolic hydroxyl group-containing compounds described for the quinonediazide group-containing compound (B).
That is, suitable 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 and other polyhydroxybenzophenones; bis (2,4-dihydroxyphenyl) Methan, bis (2,3,4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- ( 2', 4'-dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (2', 3', 4'-trihydroxyphenyl) propane, 4,4'-{1 -[4- [2- (4-Hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol and 3,3'-dimethyl-{1- [4- [2- (3-methyl-4-hydroxyphenyl) ) -2-propyl] phenyl] ethylidene} bisphenol and other bis [(poly) hydroxyphenyl] alkanes; tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxy Phenylmethane, 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)- Tris (hydroxyphenyl) methanes such as 3,4-dihydroxyphenylmethane or methyl substituents thereof; bis (3-cyclohexyl-4-hydroxyphenyl) -3- Hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy- 2-Methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl)- 4-Hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -4-hydroxyphenylmethane, bis (5-) Cyclohexyl-4-hydroxy-3-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) ) -4-Hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -2-hydroxyphenylmethane, and bis Bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes such as (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane or methyl substituents thereof; phenol, p-methoxyphenol, dimethylphenol, Examples thereof include compounds having a hydroxyl group such as hydroquinone, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, and gallic acid.

The content of the sensitizer (C) is not particularly limited as long as it does not interfere with the object of the present invention. The content of the sensitizer (C) is 10 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the novolak resin (A) because it is easy to obtain a desired effect on the cross-sectional shape of the resist film and the sensitivity. It is preferable that 13 parts by mass or more and 27 parts by mass or less is more preferable, and 15 parts by mass or more and 20 parts by mass or more is further preferable.

<Phenolic hydroxyl group-containing resin (D)>
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 of more than 1000 other than the novolak resin (A).
The positive photosensitive resin composition contains the following predetermined amount of the phenolic hydroxyl group-containing resin (D) together with the novolak resin (A) and the sensitizer (C) to form the positive photosensitive resin composition. It exhibits appropriate solubility in the developing solution, and it is easy to achieve both a good cross-sectional shape of the patterned resist film and high sensitivity without impairing the strength of the resist film.

The content of the phenolic hydroxyl group-containing resin (D) is 0.5 parts by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 9 parts by mass or less, based on 100 parts by mass of the novolak resin (A). More preferably, it is at least 8 parts by mass.

The phenolic hydroxyl group-containing resin (D) has a weight average molecular weight of more than 1000, and is not particularly limited as long as it is a resin other than the novolak resin (A). A preferable resin as the phenolic hydroxyl group-containing resin (D) is a (meth) acrylic having a structural unit derived from hydroxystyrene which may have a substituent and / or a hydroxyphenyl group which may have a substituent. Examples thereof include resins containing structural units derived from acid esters.

The phenolic hydroxyl group-containing resin (D) is derived from a structural unit derived from hydroxystyrene which may have a substituent and / or a (meth) acrylic acid ester which has a hydroxyphenyl group which may have a substituent. In the case of a resin containing a structural unit, 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 with respect to all the structural units. Preferably, 100 mol% is most preferred.

（式（Ｄ１）中、Ｒ^ｄ１は、水素原子、又は炭素原子数１以上６以下のアルキル基である。Ｒ^ｄ２は、炭素原子数１以上６以下のアルキル基、炭素原子数１以上６以下のアルコキシ基、ハロゲン原子、又はシアノ基である。ｎは、０以上４以下の整数である。ｎが２以上４以下の整数である場合、複数のＲ^ｄ２は、同一であっても異なっていてもよい。） As the structural unit derived from hydroxystyrene which may have a substituent, the structural unit represented by the following formula (D1) is preferable.

(In the formula (D1), R ^d1 is a hydrogen atom or an alkyl group ^{having 1 or more and 6 or less carbon atoms. R d2} is an alkyl group having 1 or more and 6 or less carbon atoms and 1 or more and 6 or less carbon atoms. N is an integer of 0 or more and 4 or less. When n is an integer of 2 or more and 4 or less, a plurality of R ^d2s are different even if they are the same. May be.)

The alkyl group having 1 or more and 6 or less carbon atoms is, for example, a linear or branched alkyl group having 1 or more and 6 or less carbon atoms. Linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, and neopentyl group. And so on.
The alkoxy group having 1 or more and 6 or less carbon atoms is, for example, a linear or branched alkoxy group having 1 or more and 6 or less carbon atoms. Examples of the linear or branched alkyl group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, n-pentyloxy group and isopentyl. Examples thereof include an oxy group and a neopentyloxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Preferable specific examples of the monomer giving the structural unit represented by the formula (D1) are 4-hydroxystyrene, 3-hydroxystyrene, 2-hydroxystyrene, α-methyl-4-hydroxystyrene, α-methyl. Examples thereof include -3-hydroxystyrene, α-methyl-2-hydroxystyrene, α-ethyl-4-hydroxystyrene, α-ethyl-3-hydroxystyrene, α-ethyl-2-hydroxystyrene and the like. Among these, 4-hydroxystyrene, -3-hydroxystyrene, α-methyl-4-hydroxystyrene, and α-methyl-3-hydroxystyrene are preferable, and 4-hydroxystyrene and α-methyl4-hydroxystyrene are preferable. Is more preferable.

（式（Ｄ２）中、Ｒ^ｄ２及びｎは、式（Ｄ１）におけるこれらと同様である。Ｒ^ｄ３は、水素原子、又はメチル基である。Ｒ^ｄ４は、単結合、又は炭素原子数１以上４以下のアルキレン基である。） As the structural unit derived from the (meth) acrylic acid ester having a hydroxyphenyl group which may have a substituent, the structural unit represented by the following formula (D2) is preferable.

(In the formula (D2), R ^d2 and n are the same as those in the formula (D1). R ^d3 is a hydrogen atom or a methyl group. R ^d4 is a single bond or one or more carbon atoms. It is an alkylene group of 4 or less.)

^Examples of the alkylene group as R d4 include a methylene group, an ethane-1,2-diyl group (ethylene group), an ethane-1,1-diyl group, a propane-1,3-diyl group, and a propane-1,2-diyl group. Examples include groups, propane-2,2-diyl groups, propane-3,3-diyl groups, and butane-1,4-diyl groups. Among these, a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group are preferable, and a methylene group and an ethylene group are more preferable.

Preferable specific examples of the monomer giving the structural unit represented by the formula (D2) are 4-hydroxyphenyl acrylate, 3-hydroxyphenyl acrylate, 2-hydroxyphenyl acrylate, 4-hydroxybenzyl acrylate, 3-hydroxy. Phenolic hydroxyl group-containing acrylates such as benzyl acrylate, 2-hydroxybenzyl acrylate, 4-hydroxyphenethyl acrylate, 3-hydroxyphenethyl acrylate, and 2-hydroxyphenethyl acrylate, as well as 4-hydroxyphenyl methacrylate, 3-hydroxyphenyl methacrylate, 2- Examples thereof include phenolic hydroxyl group-containing methacrylates such as hydroxyphenyl methacrylate, 4-hydroxybenzyl methacrylate, 3-hydroxybenzyl methacrylate, 2-hydroxybenzyl methacrylate, 4-hydroxyphenethyl methacrylate, 3-hydroxyphenethyl methacrylate, and 2-hydroxyphenethyl methacrylate. ..
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 is preferred, and examples thereof include 4-hydroxyphenyl acrylate, 4-hydroxybenzyl acrylate, 4-hydroxyphenyl methacrylate, and 4-hydroxybenzyl methacrylate.

When the phenolic hydroxyl group-containing resin (D) is a polymer of a monomer having an unsaturated bond, the phenolic hydroxyl group-containing resin (D) has a monomer having a phenolic hydroxyl group and a phenolic hydroxyl group. It may be a copolymer with other monomers that do not.
Examples of such other monomers include known radical polymerizable compounds and anionic polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; 2-methacryloyloxyethyl succinic acid, 2-. Methacrylic acid derivatives having carboxy groups and ester bonds such as methacryloyloxyethyl maleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (Meta) acrylic acid alkyl esters such as (meth) acrylate; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate, (Meta) acrylic acid aryl esters such as benzyl (meth) acrylate; Dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl groups such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene and vinyltoluene Aromatic compounds contained; Vinyl group-containing aliphatic compounds such as vinyl acetate; Conjugate diolefins such as butadiene and isoprene; Nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; Vinyl chloride, vinylidene chloride and the like Chlorine-containing polymerizable compounds; amide bond-containing polymerizable compounds such as acrylamide and methacrylicamide; and the like can be mentioned.

As the phenolic hydroxyl group-containing resin (D) described above, since it is easy to obtain a desired effect by using the phenolic hydroxyl group-containing resin, a resin having a structural unit derived from hydroxystyrene which may have a substituent may be used. Preferably, a resin having a structural unit derived from hydroxystyrene is more preferable, a homopolymer of hydroxystyrene is further preferable, and a homopolymer of 4-hydroxystyrene is particularly preferable.

As described above, the weight average molecular weight of the phenolic hydroxyl group-containing resin (D) is not particularly limited as long as it exceeds 1000. The weight average molecular weight of the phenolic hydroxyl group-containing resin (D) is preferably 3000 or more and 15000 or less, and more preferably 4000 or more and 13000 or less, because it is easy to obtain a positive photosensitive resin composition having particularly suitable solubility in a developing solution. More preferably, it is 5000 or more and 10000 or less.

<Other ingredients>
The positive composition may contain various additives such as a colorant, a sensitizer, an adhesion improver, a surfactant, and a plasticizer as long as the object of the present invention is not impaired.

-Sensitizer The sensitizer is not particularly limited, and can be arbitrarily selected from the sensitizers usually used in the positive photosensitive resin composition. Examples of the sensitizer include compounds having a phenolic hydroxyl group having a molecular weight of 1000 or less.

-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.

-Surfactant The positive photosensitive resin composition may contain a surfactant in order to improve coatability, defoaming property, leveling property and the like. Examples of surfactants include BM-1000, BM-1100 (manufactured by BM Chemie), Megafuck F142D, Megafuck F172, Megafuck F173, Megafuck F183 (manufactured by Dainippon Ink and Chemicals), and Florard FC-135. , Florard FC-170C, Florard FC-430, Florard FC-431 (manufactured by Sumitomo 3M), Surfron S-112, Surfron S-113, Surfron S-131, Surfron S-141, Surfron S-145 (manufactured by Asahi Glass Co., Ltd.) ), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (manufactured by Toray Silicone), BYK-310, BYK-330 (manufactured by Big Chemie Japan), etc. Silicon-based or fluorine-based surfactants can be used.

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

<Solvent>
The positive photosensitive resin composition is preferably used in the form of a solution by dissolving each of the above components in an appropriate solvent. 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 dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and Diethylene glycol dialkyl ethers such as diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Glycolalkyl ether acetates; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amylketone; Aromatic hydrocarbons such as toluene and xylene; Cyclic ethers such as dioxane; and methyl 2-hydroxypropionate, 2- Ethyl hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, Examples thereof include esters such as ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate. These solvents may be used alone or in combination of two or more.

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

<Method of preparing positive photosensitive resin composition>
The positive photosensitive resin composition can be prepared by blending each of the above components in a predetermined ratio, and then mixing and stirring by a usual method. Further, if necessary, it may be further filtered using a mesh, a membrane filter or the like.

<< Method of forming a patterned resist film >>
The patterned resist film is formed by applying the above-mentioned positive photosensitive resin composition to a substrate to form a coating film.
The process of regioselectively exposing the coating film and
The process of developing the exposed coating film with a developer and
It can be formed by a method including.

The positive photosensitive resin composition is applied to the substrate by 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. Examples of the drying method include (1) drying the coating film on a hot plate at a temperature of 80 ° C. or higher and 120 ° C. or lower for 60 seconds or longer and 120 seconds or shorter, and (2) several hours to several days at room temperature. Either the method of leaving the coating film left or (3) the method of putting the coating film in a warm air heater or an infrared heater for several tens of minutes to several hours to remove the solvent may be used. The film thickness of the coating film dried as needed is not particularly limited, but is preferably about 1.0 μm or more and 5.0 μm or less.

The type of substrate is not particularly limited. Since the above-mentioned positive photosensitive resin composition has excellent sensitivity, it can be easily applied to a substrate over a large area. For this reason, suitable substrates include substrates for displays such as liquid crystal displays and organic EL displays. Examples of the substrate for such a display include a glass plate provided with wiring such as a transparent conductive circuit and, if necessary, provided with a black matrix, a color filter, a polarizing plate, and the like.

Next, the coating film is exposed through a mask having a predetermined pattern according to the pattern shape. The exposure is performed by irradiating with active energy rays such as ultraviolet rays and excimer laser light. Examples of the light source of the active energy ray include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, an excimer laser generator, and the like. The energy dose to be irradiated varies depending on the composition of the positive photosensitive resin composition, but may be, for example, about ^{30 to 2000 mJ / cm 2.}

The exposed coating film is then developed with a developer to form a patterned resist film. Examples of the developing solution 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, and sodium phosphate.
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, or the like. Further, if necessary, the patterned resist film may be baked.

In this way, a patterned resist film made of the above-mentioned positive photosensitive resin composition is formed. Such a resist film may be used as a protective film or an insulating film, as a mask pattern for etching, or as a mold for plating.

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

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

In Examples and Comparative Examples, the following BI, B-II, and B-III were used as the quinone diazide group-containing compounds (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 quinonediazide groups in each compound (meaning how many moles of substituent OD are substituted with quinonediazide groups on average) is 2.1 mol for BI and 1.7 mol for B-II. Mol, B-III is 2.5 mol.

In Examples and Comparative Examples, the following CI and C-II were used as the sensitizers (C) (component (C)).
CI: Compound represented by the following formula C-II: Compound in which D is all hydrogen atoms in the above-mentioned B-III

As a phenolic hydroxyl group-containing resin (D) (component (D)) in Examples and Comparative Examples. The following DI and D-II were used.
DI: homopolymer of 4-hydroxystyrene (weight average molecular weight 8000)
D-II: Copolymer of 75% by mass of 4-hydroxystyrene and 25% by mass of styrene (weight average molecular weight 2500)

100 parts by mass of novolak resin (A), the quinonediazide group-containing compound (B) of the type and amount shown in Table 1, the amount of sensitizer (C) shown in Table 1, and the type and amount shown in Table 1 and The amount of the phenolic hydroxyl group-containing resin (D), the amount of 2-pyridineethanol as the adhesion enhancer shown in Table 1, and the amount of the surfactant BYK-310 (manufactured by Big Chemie) shown in Table 1 were added. The positive photosensitive resin compositions of Examples and Comparative Examples were obtained by dissolving the mixture in propylene glycol monomethyl ether acetate so that the solid content concentration was 24 mass. Using the obtained positive photosensitive resin composition, the sensitivity, cross-sectional shape, and resolution were evaluated according to the following methods. The results of these evaluations are shown in Table 1.

<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 having a film thickness of 1.5 μm.
Next, FPA-5510iv (trade name, manufactured by Canon, NA = 0.12) was used via a test chart mask (reticle) on which a mask pattern for realizing a 1.3 μm line-and-space pattern was drawn. The exposure was performed.
The exposed resist film was brought into contact with an aqueous solution of 2.38 mass% tetramethylammonium hydroxide (TMAH) at 23 ° C. for 65 seconds for development. The obtained 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, and the exposure amount at which the pattern size was 1.3 μm was confirmed. Sensitivity was evaluated according to the following criteria based on the exposure amount at which the pattern size was 1.30 μm.
⊚: The exposure amount at which the pattern size is 1.3 μm is less than ^{45 mJ / cm 2.}
◯: The exposure amount at which the pattern size is 1.3 μm is 45 mJ / cm ² or more and less than 55 mJ / cm ^2.
X: The exposure amount at which the pattern size is 1.3 μm is 55 mJ / cm ² or more.

<Cross-sectional shape>
The cross-sectional shape of the 1.3 μm line-and-space pattern obtained in the above sensitivity evaluation was observed by an SEM photograph, and the cross-sectional shape was evaluated according to the following criteria.
⊚: Rectangular shape 〇: The width near the surface of the resist pattern on the opposite side to the substrate is thicker than the width near the center in the height direction of the resist pattern, T-top shape ×: No head (cross-sectional shape is close to a triangle) Pattern shape)

<Resolution>
By the same method as the above 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 1.1 μm line and space pattern are realized. The line-and-space pattern was formed by exposure with an exposure amount capable of reproducing the 1.3 μm line-and-space pattern according to the dimensions. The obtained line-and-space pattern was observed by SEM photographs, and the resolution was evaluated according to the following criteria. When the evaluation of the cross-sectional shape was x, the evaluation was difficult, so the resolution was not evaluated.
1.3: A 1.3 μm line and space pattern can be resolved, but a 1.2 μm line and space pattern cannot be resolved.
1.2: A 1.2 μm line and space pattern can be resolved, but a 1.1 μm line and space pattern cannot be resolved.

According to Table 1, a novolak resin (A), a quinonediazide group-containing compound (B), a sensitizer (C) satisfying a predetermined requirement, and an amount of phenol satisfying a predetermined requirement and within a predetermined range. It can be seen that the positive photosensitive resin composition containing the positive hydroxyl group-containing resin (D) provides a patterned resist film having excellent sensitivity and a good cross-sectional shape.

Claims (8)

It contains a novolak resin (A), a quinonediazide group-containing compound (B), a sensitizer (C), and a phenolic hydroxyl group-containing resin (D).
The sensitizer (C) is a compound having a phenolic hydroxyl group having a molecular weight of 1000 or less.
The phenolic hydroxyl group-containing resin (D) is a resin having a weight average molecular weight of more than 1000 other than the novolak resin (A).
A positive photosensitive resin composition in which the content of the phenolic hydroxyl group-containing resin (D) is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the novolak resin (A). The phenolic hydroxyl group-containing resin (D) is a (meth) acrylic acid ester having a structural unit derived from hydroxystyrene which may have a substituent and / or a hydroxyphenyl group which may have a substituent. The positive photosensitive resin composition according to claim 1, which comprises a structural unit from which it is derived. The positive photosensitive resin composition according to claim 2, wherein the phenolic hydroxyl group-containing resin (D) is a homopolymer of hydroxystyrene. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the phenolic hydroxyl group-containing resin (D) has a weight average molecular weight of 3000 or more and 15000 or less. The positive type 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 with respect to 100 parts by mass of the novolak resin (A). Photosensitive resin composition. The quinonediazide group-containing compound (B) has the following formula (B1):

(In the formula (B1), R ^b1 is an alkyl group having 1 or more and 5 or less carbon atoms independently, and D is independently a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group. Yes, at least one of the 2 + m Ds is a 1,2-naphthoquinonediazide-5-sulfonyl group, and l and m are independently 1 or 2, respectively.)
The compound represented by and the following formula (B2):

(In formula (B2), D is a hydrogen atom or 1,2-naphthoquinonediazide-5-sulfonyl group, respectively, and at least one of the three Ds is 1,2-naphthoquinonediazide-5. -Sulfonyl group.)
The compound represented by and the following formula (B3):

(In the formula (B3), R ^b3 is independently a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms, and R ^b4 is independently a hydrogen atom, a halogen atom, and 1 carbon atom. It is an alkyl group having 6 or less, an alkoxy group having 1 or more and 6 or less carbon atoms, or a cycloalkyl group having 3 or more and 6 or less carbon atoms, and D is independently a hydrogen atom or 1,2-naphthoquinonediazide. It is a -5-sulfonyl group, and at least one of the four Ds is a 1,2-naphthoquinonediazide-5-sulfonyl group.)
The positive photosensitive resin composition according to any one of claims 1 to 5, which comprises a compound represented by. A step of applying the positive photosensitive resin composition according to any one of claims 1 to 6 to a substrate to form a coating film.
A step of regioselectively exposing the coating film and
The process of developing the exposed coating film with a developer and
A method for forming a patterned resist film, including. A patterned resist film comprising the positive photosensitive resin composition according to any one of claims 1 to 6.