KR20170064471A - Positive photoresist composition - Google Patents

Abstract

(Problem) Even when the development is carried out using a basic aqueous solution having a low pH, when the cross section of the resist pattern is observed while suppressing occurrence of scum, the side wall of the resist portion has a good shape perpendicular or substantially perpendicular to the substrate A positive type photoresist composition capable of forming a fine resist pattern easily detachable from a substrate and a photosensitive film comprising the positive type photoresist composition and a substrate having a photosensitive film, And a method of forming a patterned resist film using the same.
(A) a positive photosensitive composition comprising (A) a novolak resin and (B) a photosensitive agent, or (A ') a novolac resin containing a naphthoquinonediazide group, in a basic aqueous solution of pH 12 (A ') derived from a novolac resin (A) containing a predetermined amount of a novolac resin (A) having a predetermined structure which is soluble in a predetermined amount of the novolac resin (A) Novolac resin is used.

Description

[0001] POSITIVE PHOTORESIST COMPOSITION [0002]

The present invention relates to a positive-type photoresist composition, a substrate with a photosensitive film provided thereon with a photosensitive film comprising the positive-type photoresist composition, and a method of forming a patterned resist film using the positive-type photoresist composition.

2. Description of the Related Art As a method of manufacturing a multi-chip module such as an MCP (Multi Chip Package) or a SiP (System in Package), a plurality of IC chips are mounted on an interposer made of silicon or glass, A method of mounting the pores to the resin interposer again has been studied.

However, in this method, there is a problem in that it is expensive for an interposer made of silicon, glass, or the like, but it is difficult to mount an IC chip.

For this reason, use of a resin interposer has also been studied as an interposer for mounting an IC chip. In this case, it is necessary to form a resist pattern in order to form wirings and terminals made of a metal such as copper on the resin interposer.

 As a method for forming a resist pattern when wiring and terminals are formed on a resin substrate, a dry film made of a negative photosensitive composition is used and a basic aqueous solution of low pH (for example, pH 12 or less) Developing methods is common. As such a developer, for example, an aqueous solution of sodium carbonate is used. However, when a negative photosensitive composition is used, there is a problem such that the resolution is insufficient and the resist pattern is difficult to peel off from the resin substrate.

Therefore, as a method for solving the above problems, there is a method of forming a resist pattern by using a positive photosensitive composition having good resolution and being relatively easy to peel off from a resin substrate.

As a positive photosensitive composition which can be used for forming a wiring or a terminal made of metal, for example, a photosensitive composition comprising an alkali-soluble novolac resin such as cresol novolak resin, a photosensitizer and a benzotriazole- (See Patent Document 1).

Japanese Patent Application Laid-Open No. 2010-170612

When the negative photosensitive composition is replaced with a positive photosensitive composition in mind, it is necessary that the fine resist pattern can be satisfactorily resolved even when the photosensitive composition is developed using a basic aqueous solution having a low pH such as an aqueous solution of sodium carbonate.

However, the resolution of the positive photosensitive composition described in Patent Document 1 is not necessarily sufficient when a basic aqueous solution having a low pH is used as a developer. Further, it is desired to further improve the peelability from the substrate for the positive photosensitive composition described in Patent Document 1. [

When the positive photosensitive composition described in Patent Document 1 is used and developed with a basic aqueous solution having a low pH to form a resist pattern, when scum easily occurs or when the cross section of the resist pattern is observed, There is a problem that it is difficult to form a resist pattern having a good shape in which the side wall is perpendicular or substantially perpendicular to the substrate.

 SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a resist pattern forming method and a resist pattern forming method in which, when a development is performed using a basic aqueous solution having a low pH, A positive photoresist composition having a good shape perpendicular or substantially perpendicular to the surface of the substrate and capable of forming a fine resist pattern which is easy to peel off from the substrate and a photosensitive film comprising the positive photoresist composition, And a method for forming a patterned resist film using the positive type photoresist composition.

The present inventors have found that a positive photosensitive composition comprising (A) a novolac resin and (B) a photosensitive agent, or (A ') a novolac resin containing a naphthoquinone diazide group, in a basic aqueous solution of pH 12 (A ') derived from a novolac resin (A) containing a predetermined amount of a novolac resin (A) having a predetermined structure which is soluble in a predetermined amount of the novolac resin (A) The present inventors have found that the above problems can be solved by using a novolak resin, and have completed the present invention.

Specifically, the present invention provides the following.

A first aspect of the present invention is a photosensitive resin composition comprising (A) a novolac resin and (B) a photosensitive agent,

(A) a novolac resin comprising a phenol-derived unit and containing (A1) a novolak resin soluble in a basic aqueous solution having a pH of 12,

Wherein the ratio of the mass of the novolac resin (A1) to the mass of the novolak resin (A) is more than 50 mass%

(B) the photosensitive agent is a compound having a naphthoquinone diazide group.

A second aspect of the present invention is a positive photoresist composition comprising (A ') novolak resin having a naphthoquinone diazide group,

(A ') a novolac resin, wherein (A) a part of the phenolic hydroxyl group of the novolac resin is a compound wherein the hydrogen atom in the phenolic hydroxyl group is substituted with a group containing a naphthoquinonediazide group,

(A) a novolac resin comprising a phenol-derived unit and containing (A1) a novolak resin soluble in a basic aqueous solution having a pH of 12,

Wherein the ratio of the mass of the novolac resin (A1) to the mass of the novolac resin (A) is more than 50 mass%.

A third aspect of the present invention is a photosensitive film-attached substrate comprising a photosensitive film made of a positive type photoresist composition according to the first or second aspect.

A fourth aspect of the present invention is a photoresist composition comprising a photosensitive composition comprising a positive selective photoresist composition according to the first or second aspect,

A method for forming a patterned resist film including the development of an exposed photosensitive film.

According to the present invention, even when the development is carried out using a basic aqueous solution having a low pH, when the cross section of the resist pattern is observed while suppressing the generation of scum, the side wall of the resist portion is preferably a vertical A positive photoresist composition capable of forming a fine resist pattern which is easy to peel off from a substrate and which has a shape of a positive photoresist composition and a photosensitive film composed of the positive photoresist composition, A method of forming a patterned resist film using the photoresist composition of the present invention can be provided.

≪ Positive type photoresist composition >

The positive photoresist composition (hereinafter also referred to as a resist composition) is a first positive photoresist composition or a second positive photoresist composition described below.

The first positive type photoresist composition comprises (A) a novolak resin and (B) a photosensitizer. The novolac resin (A) includes (A1) novolak resin. (A1) The novolac resin contains a unit derived from phenol, and is soluble in a basic aqueous solution having a pH of 12 or less.

The ratio of the mass of the novolak resin (A1) to the mass of the novolak resin (A) is more than 50 mass%.

The photosensitive agent (B) is a compound having a naphthoquinone diazide group.

The second positive type photoresist composition includes (A ') novolak resin having a naphthoquinone diazide group.

(A ') The novolak resin is a resin in which, in a part of the phenolic hydroxyl groups of the novolak resin (A), the hydrogen atom in the phenolic hydroxyl group is substituted with a group containing a naphthoquinone diazide group.

(A ') The novolac resin (A) which is a precursor of the novolak resin includes (A1) novolak resin. (A1) The novolac resin contains a unit derived from phenol, and is soluble in a basic aqueous solution having a pH of 12 or less.

The ratio of the mass of the novolak resin (A1) to the mass of the novolak resin (A) is more than 50 mass%.

Hereinafter, the first positive photoresist composition and the second positive photoresist composition will be described in order.

[First positive photoresist composition]

Hereinafter, essential or optional components and a method of preparing a positive photoresist composition with respect to the first positive photoresist composition will be described.

≪ (A) Novolak resin >

(A) Novolak resin (hereinafter also referred to as component (A)) is an alkali-soluble novolak resin. The novolac resin (A) contains a unit derived from phenol and essentially contains (A1) novolak resin soluble in a basic aqueous solution having a pH of 12.

Here, the fact that the novolak resin is soluble in a basic aqueous solution having a pH of 12 means that a novolak resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20 mass% And when the resin film is immersed in a basic aqueous solution of pH 12 at 20 to 30 ° C for 1 minute, it means that the resin film is dissolved by 0.1 μm or more.

The amount of the novolak resin (A1) in the novolak resin (A) is more than 50% by mass. (A) Novolak resin contains such a positive amount of (A1) novolak resin, even when a basic developer having a low pH such as a pH of 12 or less is used, the occurrence of scum It is possible to form a fine resist pattern having a good shape in which the side wall of the resist portion is perpendicular or substantially perpendicular to the substrate.

The amount of the novolac resin (A1) in the novolak resin (A) is preferably from 55 to 90 mass%, more preferably from 60 to 80 mass%, from the viewpoint of easily forming a resist pattern having a better shape.

The mass average molecular weight (Mw) of the novolac resin (A1) in terms of polystyrene is preferably from 1,000 to 30,000, more preferably from 3,000 to 20,000, from the viewpoint of solubility in a basic aqueous solution having a low pH.

(A1) The degree of dispersion (mass average molecular weight (Mw) / number average molecular weight (Mn)) of the novolac resin is preferably from 2 to 20, more preferably from 3 to 15.

The novolak resin (A) preferably contains (A2) a novolak resin together with (A1) a novolac resin. (A2) The novolak resin is a novolac resin containing a unit derived from an alkylphenol, insoluble in a basic aqueous solution having a pH of 13 but soluble in a basic aqueous solution having a pH of more than 13.

Here, the fact that the novolac resin is insoluble in a basic aqueous solution having a pH of 13 means that a novolak resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20 mass% And when the resin film is immersed in a basic aqueous solution having a pH of 13 at 20 to 30 DEG C for 1 minute, the resin film is soluble in less than 0.1 mu m.

The fact that the novolac resin has solubility in a basic aqueous solution having a pH of more than 13 means that a resin film having a thickness of 1 占 퐉 is formed on a substrate (substrate) with a novolak resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20 mass% And when the resin film is immersed in a basic aqueous solution having a pH of more than 13 at 20 to 30 DEG C for 1 minute, it means that the resin film is dissolved by 0.1 mu m or more.

When the (A) novolak resin contains (A2) novolac resin, even when the resist is developed using a basic aqueous solution having a low pH, the first resist composition can be used to suppress generation of scum, It is easy to form a fine resist pattern having a good shape perpendicular or substantially perpendicular to the substrate.

(A2) The mass average molecular weight (Mw) of the novolak resin in terms of polystyrene is preferably from 500 to 30,000, more preferably from 1,000 to 20,000, from the viewpoint of easily forming a resist pattern of a good shape.

When the novolac resin (A) contains the novolak resin (A2), the content of the novolac resin (A2) in the novolac resin (A) is preferably from 1 to 45% by mass, more preferably from 5 to 40% Is more preferable.

 In the first resist composition, the novolac resin (A) may contain a novolac resin other than the novolak resin (A1) and the novolak resin (A2) within the range that does not impair the object of the present invention .

The ratio of the mass of the novolak resin (A1) to the total mass of the mass of the novolak resin (A2) in the mass of the novolak resin (A) is preferably 80 mass% or more, more preferably 90 mass% or more , And particularly preferably 100 mass%.

The novolak resin (A) is not particularly limited, but is preferably obtained by condensation reaction of a condensing agent such as an aldehyde in an amount of 0.5 to 1.0 mol per 1 mol of phenols under an acidic catalyst.

(A1) The novolak resin is prepared by using phenols containing a desired amount of phenol. (A2) The novolak resin is prepared using phenols containing a desired amount of alkylphenol.

The phenols include, for example, cresols such as phenol, o-cresol, m-cresol and p-cresol; Such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5- Ylenol; ethylphenol, m-ethylphenol, p-ethylphenol and the like, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m- Phenol 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; (All of the above alkyl groups have 1 to 4 carbon atoms),? -Naphthol,? -Naphthol, hydroxydiphenyl, bisphenol A, and the like. These phenols may be used alone or in combination of two or more.

As the condensation agent, aldehydes and ketones can be mentioned, but aldehydes, in particular formaldehyde and paraformaldehyde, are preferred.

Examples of the acidic catalyst include, but are not limited to, 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 the like. These acidic catalysts may be used alone or in combination of two or more.

(A1) The novolak resin is prepared by using, for example, (A1) a phenol containing a positive phenol such that the amount of units derived from phenol in the novolak resin is 50 mass% or more.

The content of units derived from phenol in the (A1) novolak resin is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and 90% , And most preferably 100 mass%.

In short, the novolak resin (A1) is most preferably composed of only units derived from phenol.

Examples of the compound other than phenol which may be contained in the phenol used in the preparation of the (A1) novolac resin include (A1) a compound obtained by dissolving o-cresol, m-cresol, , Resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and fluoroglycinol.

(A2) The novolak resin is prepared by using phenols including an alkylphenol. Examples of the alkylphenol include o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6- , O-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o- Butylphenol, m-butylphenol, p-butylphenol, p-tert-butylphenol, 2,3,5-trimethylphenol and 3,4,5-trimethylphenol.

The phenols used in the preparation of the novolac resin (A2) may contain two or more kinds of alkyl phenols in combination.

(A2) The content of the alkylphenol in the phenol used in the preparation of the novolac resin is preferably from 0.01 to 5 parts by weight, based on the kind of the alkylphenol, so that the resulting (A2) novolak resin exhibits desired solubility in a basic aqueous solution having a pH of more than 13 .

Typically, the amount of units derived from alkylphenol in the (A2) novolac resin is preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 90% by mass or more, % Is most preferable.

Among the alkylphenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination.

The novolak resin (A2) is preferably a resin prepared using a phenol resin which is a mixture of m-cresol and p-cresol.

(A2) a novolak resin is prepared by using phenols including m-cresol and p-cresol, by adjusting the blending ratio of the (A2) novolac resin, the sensitivity and heat resistance And so on.

The mixing ratio of m-cresol and p-cresol is not particularly limited, but m-cresol / p-cresol = 3/7 to 8/2 (mass ratio) is preferable.

In a part of the phenolic hydroxyl group of the novolac resin (A), the hydrogen atom in the phenolic hydroxyl group may be substituted with a group containing a naphthoquinonediazide group. The group containing a naphthoquinone diazide group is not particularly limited, but it is preferably a naphthoquinone diazide sulfonyl group in that novolakin diazide group-containing (A) novolak resin can be easily prepared.

The novolak resin (A) novolak resin having a naphthoquinone diazide group may be obtained, for example, when the group containing a naphthoquinonediazide group is a naphthoquinonediazide sulfonyl group, (A) the phenolic hydroxyl group of the novolac resin, And then condensing a predetermined amount of naphthoquinonediazide sulfonyl chloride.

In addition, it is preferable to add at least one resin selected from novolac resins (A1), (A2) novolak resins, and (novolac resins other than (A1) A plurality of novolak resins having a naphthoquinone diazide group may be incorporated in the first resist composition, and a novolak resin having a naphthoquinone diazide group and a novolak resin having no naphthoquinone diazide group Resin may be added to the first resist composition.

The proportion of the novolac resin (A) in which the hydrogen atom of the phenolic hydroxyl group is substituted with a group containing a naphthoquinone diazide sulfonyl group is preferably 2 to 10 mol%, more preferably 3 to 7 mol %, More preferably 3 to 5 mol%.

The content of the novolak resin (A) in the first resist composition is not particularly limited within the range not hindering the object of the present invention. The content of the novolak resin (A) is preferably from 60 to 95 mass%, more preferably from 70 to 95 mass%, and particularly preferably from 80 to 90 mass%, based on the mass of the solid content of the first resist composition.

<(B) Photosensitizer>

The first resist composition includes (B) a photosensitizer (hereinafter also referred to as a component (B)). (B) is a compound having a naphthoquinonediazide group. Examples of the component (B) include naphthoquinonediazide esters. The naphthoquinone diazide ester compound is not particularly limited as long as it is generally used as a photosensitizer in a positive type photoresist composition and may be used alone or in combination of two or more.

For example, an esterified product of a phenol compound represented by the following formula (1) and a naphthoquinone diazidesulfonic acid compound can be used.

[Chemical Formula 1]

(In the formula (1), R ¹ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms Alkyl group.

R ¹² to R ¹⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

And R ¹¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by the following formula (2):

(2)

, R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 3 to 3 carbon atoms To 6, and c represents an integer of 1 to 3.

When Q ¹ is coupled with the terminal of R ¹¹ it is, Q ^1, together with the carbon atoms between R ^11, and Q ¹ and R ^11, represents a cycloalkyl group of a carbon atom number of 3-6.

a and b each represent an integer of 1 to 3, and d and e represent an integer of 0 to 3.

x and y are integers of 0 to 3, and x + y = 0 to 3)

Among the phenol compounds represented by the formula (1), particularly preferred compounds are the compounds represented by the following formula (3).

(3)

In addition, esters of phenolic compounds and naphthoquinone diazidesulfonic acid compounds shown below are also preferably used.

Preferred phenolic compounds other than the compound represented by the formula (3) include, for example,

Hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4- (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) Hydroxyphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) Dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis Dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis 2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl- Trisphenol-type compounds such as 4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane and bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane;

(2,5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenol, 2,6-bis Linear type 3-core phenol compounds;

Bis [3- (2-hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane, bis [2,5- Hydroxybenzyl) -4-hydroxyphenyl] methane, bis [3- (3,5-dimethyl 4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5- Hydroxyphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4- Hydroxyphenyl] methane, bis [2-hydroxy-3- (2-hydroxy-3- Methylbenzyl) -5-methylphenyl] methane, bis [4-hydroxy-3- (2-hydroxy- 3- (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane 4-nucleophile phenolic compounds;

Bis [4-hydroxy-3- (4-hydroxvbenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4- 5-methylbenzyl] -6-cyclohexylphenol, 2,6-bis [2,5-dimethyl-3- (2-hydroxy- Linear type pentene compounds such as linear phenolic compounds such as methylphenol;

Bis (2,3-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4'- Dihydroxyphenyl) -2- (2 ', 4' -trihydroxyphenyl) propane, 2- (2, Hydroxyphenyl) propane, 2- (4-hydroxyphenyl) propane, 2- (3-fluoro-4- 2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) propane, Hydroxyphenyl) propane, 2- (2, 3, 4-trihydroxyphenyl) -2- (4'-hydroxy-3 ', 5'- And the like;

1- [1- (3-methylphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] ) Isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene;

And condensed phenol compounds such as 1,1-bis (4-hydroxyphenyl) cyclohexane.

These may be used alone or in combination of two or more.

The phenolic hydroxyl groups described above may be all or part of the phenolic hydroxyl groups as long as they are esterified, and the esterification can be carried out by a conventional method. For example, a method of condensing naphthoquinone diazide sulfonyl chloride with the phenol compound described above can be mentioned.

For example, when a phenol compound and naphthoquinone-1,2-diazide-4 (or 5) -sulfonyl chloride are reacted in an organic solvent such as dioxane, n-methylpyrrolidone, dimethylacetamide, tetrahydrofuran , And then a basic catalyst such as triethylamine, triethanolamine, pyridine, alkali carbonate or alkali hydrogen carbonate is added to the reaction mixture, and the obtained product is washed with water and dried to obtain a component (B) The naphthoquinonediazide esters to be used can be prepared.

The esterification ratio in the naphthoquinone diazide esterified product is not particularly limited, but is preferably 20 to 80%, more preferably 30 to 70%. When the esterification rate is less than 20%, the resolution is degraded.

The esterification rate is the ratio of the esterified hydroxyl groups in the molar number of hydroxyl groups used for preparing the naphthoquinone diazide ester compound.

As the component (B), besides the naphthoquinone diazide ester compounds described above, for example, esterification reaction products of a phenol compound such as polyhydroxybenzophenone and alkyl gallate and a naphthoquinone diazidesulfonic acid compound can also be used .

The content of the naphthoquinone diazide ester compound derived from a phenol compound such as polyhydroxybenzophenone or alkyl gallic acid in the component (B) is 80 mass% or less, particularly 50 mass% or less, It is preferable in terms of improvement of the effect.

The amount of the component (B) in the first resist composition differs depending on the type of the photosensitizer. Typically, the content of the component (B) is preferably 5 to 40 mass%, more preferably 10 to 20 mass%, with respect to the mass of the component (A).

&Lt; (C) High boiling point compound &gt;

The first resist composition may contain a high boiling point organic compound (hereinafter also referred to as (C) component) having a boiling point of 180 ° C or higher under atmospheric pressure, as required. The boiling point of the component (C) under atmospheric pressure is preferably 200 to 350 占 폚. The component (C) is preferably water-soluble.

The component (C) is in a liquid state under atmospheric pressure. Therefore, the solid content in the first resist composition does not include the component (C).

The first resist composition contains at least one kind of the component (C), so that the film density of the film made of the first resist composition can be reduced.

Therefore, when the first resist composition containing the component (C) is used, even in the case of developing using a basic aqueous solution having a low pH, even on a substrate, particularly a substrate having a step on the surface, , It is easy to form a resist pattern having an excellent perpendicularity to the substrate of the pattern side wall.

It is also preferable that a good photoresist pattern can be formed without depending on the conditions (heating time, heating means, etc.) of the prebaking treatment and the PEB (post-exposure baking) treatment.

Examples of the high boiling point compound (C) include benzoic acid, salicylic acid, salicylic acid, methyl salicylate, benzyl salicylate, diethyl phthalate, dibutyl phthalate, dimethyl phthalate,? -Butyrolactone, ethyl benzoate, Propylene glycol monohexyl ether, 1,3-octylene glycol, diethylene glycol, diethylene glycol diacetate, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol monomethyl ether, diethylene glycol monohexyl ether, Ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, dipropylene glycol, dipropylene glycol monobutyl ether, , Triethylene glycol di-2-ethyl butyrate, triethylene glycol dimethyl ether, triethylene glycol Diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, 2-ethylhexanoic acid, caprylic acid, caproic acid, catechol, octylphenol, N- .

These may be used singly or in combination of two or more. Among them, the boiling point is preferably 250 to 350 ° C, and benzyl salicylate is particularly preferable.

The content of the high boiling point compound (C) in the first resist composition is preferably 1 to 30% by mass relative to the total mass of the mass of the component (C) and the mass of the (S) solvent contained in the first resist composition , More preferably from 5 to 20 mass%. When the first resist composition contains (C) a high boiling point compound in such a range of amounts, particularly when a basic aqueous solution having a low pH is used for development, the occurrence of scum is suppressed, It is easy to form a resist pattern having excellent properties.

<(S) Solvent>

The first resist composition is preferably used in the form of a solution in which each of the above components is dissolved in an appropriate (S) solvent. As such (S) solvent, a solvent which does not correspond to the above-mentioned (C) high boiling point compound is used. In short, in the first resist composition, the (S) solvent is defined as a solvent component not containing the component (C).

Examples of the (S) solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; Monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate or monomethyl ether, Polyhydric alcohols, and derivatives thereof; Cyclic ethers such as dioxane; And esters such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate. These may be used alone or in combination of two or more.

The (S) solvent may be used alone or in combination of two or more kinds.

The amount of the (S) solvent to be used is preferably an amount such that the solid content concentration of the first resist composition is 20 mass% or more and 65 mass% or less, for example. Further, as described above, the solid component of the first resist composition does not contain the component (C). In this case, it is easy to easily form a coating film having a film thickness of 3 占 퐉 or more by the spin coat method.

&Lt; Other components &gt;

The first resist composition may contain, in addition to the components described above, various additives conventionally mixed with the positive resist composition as other components. Specific examples of the other components include a sensitivity improving agent (sensitizer) and an adhesion improver for improving adhesion with a substrate.

· Sensitizer

The sensitivity improving agent is not particularly limited and known sensitizing agents can be used.

Examples of the sensitivity enhancer include bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, 1,4-bis [1- (3,5- Bis (3,5-dimethyl-4-hydroxyphenylmethyl) -6-methylphenol, bis (4-hydroxy-3,5-dimethylphenyl) -2- Hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy- Methane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] Hydroxyphenyl) ethyl] benzene, 2,6-bis [1- (2,4-dihydroxyphenyl) isopropyl] (4-hydroxyphenyl) isopropyl] resorcin, 4,6-bis (3,5-dimethoxy-4-hydroxyphenylmethyl) pyrogallol , 4,6-bis (3,5-dimethyl-4-hydroxyphenylmethyl) (2,5-dimethyl-4-hydroxyphenylmethyl) -4-methylphenol, 2,6-bis (3-methyl-4,6-dihydroxyphenylmethyl) -4- Methylphenol, 2,6-bis (2,3,4-trihydroxyphenylmethyl) -4-methylphenol, and 1,1-bis (4-hydroxyphenyl) cyclohexane.

· Adhesion improver

Examples of the adhesion improving agent include adhesion improvers described in JP-A-62-262043 and JP-A-11-223937.

Concrete examples of the adhesion improver include 6-methyl-8-hydroxyquinoline, 6-ethyl-8-hydroxyquinoline, 5-methyl-8-hydroxyquinoline, 8-hydroxyquinoline, 4-hydroxyphthalidine, 2,4-dihydroxypheteridine, 4-hydroxyphthyridine-2-sulfonic acid, 2-ethyl- 1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 3,8-dimethyl-1,10-phenanthroline, 3,8-dihydroxy- , 10-phenanthroline, 5-carboxy-1,10-phenanthroline, 5,6-dihydroxy-1,10-phenanthroline, 1,10-phenanthroline- '-Dimethyl-2,2'-bipyridyl, 2,2'-bipyridyl, 2,2'-bipyridyl-5-carboxylic acid, 5,5'-dichloro- Pyridyl, 3,3'-dihydroxy-2,2'-bipyridyl, 3,3'-dimercapto-2,2'-bipyridyl and the like.

The aromatic heterocyclic compound having at least one of the bonds represented by the following formulas (4) and (5) and at least one bond represented by the following formula (6) is mixed on the ring, The adhesion of the resist composition to the substrate can be remarkably increased.

[Chemical Formula 4]

[Chemical Formula 5]

(In the formula (5), R ¹⁸ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms)

[Chemical Formula 6]

(In the formula (6), R ¹⁹ represents a linear or branched alkyl group having 1 to 5 carbon atoms substituted with a hydroxyl group or a hydroxyl group)

 As the heterocyclic compound, there can be mentioned, for example, &quot; Organic Compound Structural Index &quot; (published on Dec. 20, 1973, Maruzen Co., Ltd.) 362-401, indoline-based compounds, indigo-based compounds, and the like; Having 6 atoms of a nitrogen atom skeleton such as a pyridine-based compound, a quinoline compound, a hydroquinoline compound, an isoquinoline compound, an acridine compound, a benzoquinoline compound, a naphthoquinoline compound or a phenanthroline compound Thing; Having a five-atom cyclic skeleton of two nitrogen atoms such as a pyrazole-based compound, an imidazole-based compound, an imidazoline-based compound, and a benzimidazole-based compound; Having a six-atom cyclic skeleton of two nitrogen atoms such as a diazide compound, a hydropyridine compound, a benzodiazine compound, and a dibenzodiazine compound; Triazole-based compounds, benzotriazole-based compounds, and the like; A triazine-based compound, and the like; Having a five-membered ring skeleton of four nitrogen atoms such as tetrazole and pentetrazole; Having a six-membered ring skeleton of four nitrogen atoms such as 1,2,4,5-tetrazine; Other purine-based compounds, pteridine-based compounds, allo-based compounds, 2H-pyrrole, and the like can be given.

Among them, the compound represented by the following formula (7) is preferable in view of being able to inhibit the generation of scum and to provide a positive-type photoresist composition excellent in adhesiveness to a substrate, particularly 2- Hydroxyethyl) pyridine are preferred.

(7)

(In the formula (7), k represents an integer of 1 to 3, and R ²⁰ represents a linear or branched alkyl group having 1 to 5 carbon atoms substituted with a hydroxyl group or a hydroxyl group.

The content of the adhesion improver in the first resist composition is preferably 0.1 to 1.0% by mass, more preferably 0.2 to 0.7% by mass based on the total mass of the solid content of the first resist composition. When the first resist composition contains such an amount of the adhesion improver, the first resist composition tends to be well adhered to the substrate, and both the good resolution and the suppression of scum formation after development are compatible with each other.

The first resist composition may contain the following components in addition to the sensitivity improving agent and the adhesion improving agent.

The first resist composition is preferably at least one selected from the group consisting of p-toluenesulfonic acid chloride (PTSC), 4,4'-bis (diethylamino) benzophenone, 1,4-bis Isopropyl] benzene, 1,3-bis [1- (2-methyl-4-hydroxy-5-cyclohexylphenyl) ] Benzene, and the like.

The content of these components in the first resist composition is preferably in the range of about 0.01 to 10 mass% with respect to the total mass of the composition.

The first resist composition contains a compatibilizing additive such as an ultraviolet absorber for preventing halation (for example, 4-dimethylamino-2 ', 4'-dihydroxybenzophenone, 5-amino- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4'-hydroxyazobenzene, 4-diethylamino-4'-ethoxyazobenzene, 4,4'-diethylaminoazobenzene (For example, Fluoride FC-430, FC431 (trade name, manufactured by Sumitomo 3M Ltd.), Eftop EF122A, EF122B, EF122C and EF126 (trade name, (A fluorochemical surfactant such as Megapak R-08 (manufactured by Dainippon Ink and Chemicals, Inc.)) and the like may be included in the range not hindering the object of the present invention.

&Lt; Method for preparing first resist composition &gt;

The first resist composition is prepared by uniformly stirring and mixing the components described above. When the first resist composition is prepared, it may be dispersed and mixed with a disperser such as a dissolver, a homogenizer, or a three roll mill, if necessary. Further, after mixing, filtration may be further performed using a mesh, a membrane filter, or the like.

[Second positive type photoresist composition]

Hereinafter, with respect to the second positive photoresist composition, essential or optional components and a method of preparing the positive photoresist composition will be described.

In addition, in the second resist composition, the (S) solvent is defined as a solvent component not containing the component (C), and the solid component of the second resist composition contains the component (C) It does not.

&Lt; (A ') Novolac resin &gt;

The second resist composition essentially comprises (A ') novolak resin (hereinafter also referred to as component (A')). (A ') The novolac resin is a novolak resin having a naphthoquinone diazide group.

Therefore, the novolak resin (A ') has both a role as a novolak resin and a role as a photoresist (B) in the second resist composition.

(A ') The novolak resin is a resin in which, in a part of the phenolic hydroxyl groups of the novolak resin (A), the hydrogen atom in the phenolic hydroxyl group is substituted with a group containing a naphthoquinone diazide group.

(A ') The novolac resin (A) which is a precursor of the novolak resin includes (A1) novolak resin. (A1) The novolac resin contains a unit derived from phenol, and is soluble in a basic aqueous solution having a pH of 12 or less.

Namely, the novolak resin (A1) is the same as the novolac resin (A1) contained in the first resist composition.

The ratio of the mass of the novolak resin (A1) to the mass of the novolak resin (A) is more than 50 mass%. By using (A) a novolak resin prepared using (A) a novolak resin containing (A1) a novolak resin in such proportion, a basic developer of low pH such as a pH of 12 or lower is used Even when the first resist composition is used, it is possible to form a fine resist pattern having a good shape in which the sidewalls of the resist portion are perpendicular or substantially perpendicular to the substrate, while suppressing occurrence of scum.

As described above, the novolak resin (A1) includes a unit derived from phenol, and it is preferable that the content of the unit derived from phenol (A1) in the novolak resin and the content of the unit derived from phenol The units other than the unit derived from phenol to be used are the same as the novolak resin (A1) contained in the first resist composition.

(A) The novolac resin (A) which is a precursor of the novolac resin preferably contains (A2) novolak resin together with (A1) novolak resin. (A2) The novolak resin is the same resin as the novolac resin (A2) described for the first resist composition.

(A2) novolac resin content in the novolak resin (A), the content of the novolak resin (A1) in the novolak resin (A) and the content of the novolak resin (A2) 1 &lt; / RTI &gt;

When the novolac resin (A ') is a resin derived from a novolac resin (A) comprising a novolak resin (A1) and a novolac resin (A2), and is developed using a basic aqueous solution having a low pH , It is easy to form a fine resist pattern having a good shape in which the sidewall of the resist portion is perpendicular or substantially perpendicular to the substrate while suppressing the occurrence of scum by using the second resist composition.

The method for preparing a novolak resin by introducing a group containing a naphthoquinonediazide group into the novolak resin (A) (A ') is not particularly limited as long as the method for preparing the novolac resin having the naphthoquinonediazide group (A) Is the same as the preparation method of novolak resin.

The ratio of the hydrogen atom of the phenolic hydroxyl group in the novolak resin (A ') substituted with the group containing a naphthoquinone diazide sulfonyl group is preferably 2 to 10 mol%, more preferably 3 to 7 mol% Mol%, more preferably 3 to 5 mol%.

The preferred content of the novolak resin (A ') in the second resist composition is the same as the preferred content of the novolac resin (A) in the first resist composition.

<(B) Photosensitizer>

Since the second resist composition contains the above-mentioned (A ') novolak resin, (B) a photoresist may not necessarily be included. However, the second resist composition may contain (B) a photosensitizer.

The type and amount of the photosensitive agent (B) that may be contained in the second resist composition are the same as those of the first resist composition.

&Lt; (C) High boiling point compound &gt;

The second resist composition may contain the same amount of the high boiling point compound (C) as the first resist composition, the same amount as the first resist composition.

<(S) Solvent>

The second resist composition may contain the same amount of the (S) solvent as the first resist composition in the same amount as the first resist composition.

&Lt; Other components &gt;

The second resist composition may contain other components of the same kind as described for the first resist composition in the same amount as the first resist composition.

&Lt; Method for preparing second resist composition &gt;

The second resist composition can be prepared in the same manner as the first resist composition.

<< Photosensitive film-attached substrate >>

 The photosensitive film-adhered substrate is provided with a photosensitive film comprising the first resist composition or the second resist composition described above on a substrate.

The method of forming the photosensitive film on the substrate is not particularly limited. For example, a photosensitive film can be formed on a substrate by applying a first resist composition or a second resist composition using a spinner or the like, followed by drying.

The photosensitive film may be formed on the substrate by sticking a photosensitive dry film prepared according to a conventional method using the first resist composition or the second resist composition onto the substrate.

The film thickness of the photosensitive film is not particularly limited and is appropriately determined depending on the use of the resist pattern formed using the photosensitive film. Typically, the thickness of the photosensitive film is preferably 1 to 20 mu m, more preferably 3 to 10 mu m.

The material of the substrate is not particularly limited. An inorganic material such as Si, Cu, Au, and glass, or an organic material such as a resin.

In view of reducing the manufacturing cost of a multi-chip module such as an MCP (Multi Chip Package) or a SiP (System in Package), and easily mounting an IC chip on an interposer when a multi-chip module is manufactured, Is preferably a resin material.

The photosensitive film-attached substrate having the resin substrate can be preferably used as an IC chip-mounting interposer used for manufacturing a multi-chip module.

<< Method of forming a patterned resist film >>

A method for forming a patterned resist film is a method for selectively performing positional exposure of a photosensitive film comprising a first resist composition or a second resist composition,

And developing the exposed photosensitive film.

A photosensitive film is usually formed on a substrate. The material of the substrate, the method of forming the photosensitive film, and the film thickness of the photosensitive film are the same as those described for the substrate with the photosensitive film.

For the photosensitive film formed as described above, position selective exposure is performed in accordance with a desired pattern shape. The position selective exposure is performed by, for example, a method of exposing through a light-shielding mask.

As a light source used for exposure, a low-pressure mercury lamp, a high-pressure mercury lamp, and an ultra-high-pressure mercury lamp which emit light near wavelengths of 365 nm (i line), 405 nm (h line), and 435 nm .

After the exposure, the photosensitive film may be subjected to post-exposure baking (PEB) at a temperature of 80 to 150 캜 for 40 seconds to 600 seconds, preferably 60 seconds to 360 seconds, if necessary.

Examples of active lines used for exposure include ArF excimer lasers, KrF excimer lasers, F2 excimer lasers, extreme ultraviolet (EUV) light sources, and the like, in addition to the g line, h line, and i line by the low pressure mercury lamp, high pressure mercury lamp, , Vacuum ultraviolet (VUV), electron beam (EB), X-ray, and soft X-ray.

Then, development of the exposed photosensitive film is performed. The type of the developer is not particularly limited, and various basic aqueous solutions conventionally used as a developer for forming a resist pattern can be used as a developer.

It is preferable to use a basic aqueous solution having a low pH (for example, a pH of 12 or less) as the developing solution in terms of facility for forming a resist pattern using the negative photosensitive composition, As a basic aqueous solution having a low pH, it is preferable to use an aqueous solution of sodium carbonate. For sodium carbonate aqueous solution, the concentration of sodium carbonate is preferably 5 mass% or less.

The development is carried out at a temperature of, for example, 20 to 30 占 폚. The patterned resist film obtained after development is rinsed with pure water or the like, and then dried.

After the development, the patterned resist film may be baked (post-baked).

According to the method described above, since the above-described first resist composition or second resist composition is used, even when development is performed using a basic aqueous solution having a low pH, It is possible to form a fine resist pattern having a good shape in which the sidewall of the resist portion is perpendicular or substantially perpendicular to the substrate and which is easy to peel off from the substrate.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[Preparation Example 1]

465 g of a formalin aqueous solution having a concentration of 37% by mass and 2 g of oxalic acid were added to 1000 g of the phenol in the reaction vessel. The contents of the reaction vessel were heated to a refluxing state and then subjected to polymerization reaction under reflux until the molecular weight reached a predetermined value. Subsequently, the reaction vessel was heated under atmospheric pressure until the inner temperature of the reaction vessel reached 170 DEG C, thereby dehydrating the contents of the reaction vessel. Under reduced pressure, the reaction vessel was heated until the inner temperature of the reaction vessel reached 200 占 폚 to remove moisture and residual monomer from the contents of the reaction vessel. The contents of the reaction vessel were recovered to obtain a novolac resin (NV1) having a mass average molecular weight of 8,000. NV1 was soluble in a basic aqueous solution having a pH of 12.

[Preparation Example 2]

100 g of a mixture of m-cresol and p-cresol (mass ratio, m-cresol: p-cresol = 60: 40) was injected into the reaction vessel. Then, 465 g of a formalin aqueous solution having a concentration of 37% by mass and 2 g of oxalic acid were added to the reaction vessel. The contents of the reaction vessel were heated to a refluxing state and then subjected to polymerization reaction under reflux until the molecular weight reached a predetermined value. Subsequently, the reaction vessel was heated under atmospheric pressure until the inner temperature of the reaction vessel reached 170 DEG C, thereby dehydrating the contents of the reaction vessel. Under reduced pressure, the reaction vessel was heated until the inner temperature of the reaction vessel reached 200 占 폚 to remove moisture and residual monomer from the contents of the reaction vessel. The contents of the reaction vessel were recovered to obtain a novolac resin (NV2) having a mass average molecular weight of 5900. NV2 was insoluble in a basic aqueous solution having a pH of 13 and had solubility in a basic aqueous solution having a pH of more than 13.

[Preparation Example 3]

50 g of novolak resin (NV1) and 4 g (0.015 mol) of 1,2-naphthoquinonediazide-4-sulfonic acid chloride were charged into a reaction vessel. To the reaction vessel, 162 g of dioxane was added to dissolve the contents of the reaction vessel. Then, 3.0 g (0.030 mol) of triethylamine was added to the dropping funnel, and the contents of the reaction vessel were stirred at room temperature for 1 hour.

Thereafter, 1.63 g (0.045 mol) of hydrochloric acid was added to the reaction vessel, and stirring was further continued at room temperature for 30 minutes, followed by filtration to obtain a reddish brown liquid.

The obtained reddish brown liquid was added to a 2-liter beaker containing 1 liter of pure water while stirring to precipitate a precipitate.

The resulting solid was dissolved in propylene glycol monoethyl ether acetate, and the solution was concentrated to obtain 3.8 mol% of the entire phenolic hydroxyl group of NV1, which was substituted with 1,2-naphthoquinone diazide sulfonyl group To obtain a concentrated solution of the novolac resin (NV3).

[Examples 1 to 4 and Comparative Examples 1 to 3]

In Examples and Comparative Examples, NV1, NV2 and NV3 obtained in Preparative Examples 1 to 3 were used as the novolak resin as the component (A) or the component (A ').

As the component (B), among the phenolic hydroxyl groups having 1 mole of 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] A photosensitizer in which the hydrogen atom of the hydroxyl group of the moles was substituted with a 1,2-naphthoquinonediazide-4-sulfonyl group was used.

As component (C),? -Butyrolactone (boiling point 204 占 폚 under atmospheric pressure) was used.

As the (S) solvent, propylene glycol monoethyl ether acetate was used.

The component (A) of the kind and amount shown in Table 1 and the component (B) and the component (C) in the amount shown in Table 2 were dissolved in propylene glycol monoethyl ether acetate so as to have a solid content concentration of 33 mass% , The positive photoresist compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were obtained.

Using the obtained positive photoresist composition, the resolution, the generation of scum, the perpendicularity of the side wall of the resist pattern to the substrate, and the peelability of the resist pattern from the substrate were evaluated by the following method. The results of these evaluations are shown in Table 1.

&Lt; Evaluation of resolution &gt;

A positive photoresist composition was applied on a copper substrate using a spinner to form a coating film. The coated film was dried at 100 캜 for 240 seconds to form a photosensitive film having a thickness of 5 탆. Subsequently, a line-and-space pattern having a mask size of 5 占 퐉 was formed on the photosensitive film through a mask having a predetermined shape and dimensions using a reduced projection exposure apparatus (NSR-2205I14E, manufactured by Nikon Corporation, NA = 0.50) And then exposed for 0.1 to 3 seconds.

Subsequently, the exposed photosensitive film was immersed in an aqueous solution of sodium carbonate having a concentration of 1.5% by mass at 23 占 폚 for 120 seconds, followed by rinsing with water for 30 seconds and drying to obtain a resist pattern.

The formed resist pattern was observed with an optical microscope and a scanning electron microscope (SEM), and the case where the line and space pattern of a predetermined dimension was resolvable was evaluated as &amp; cir &amp;, the line and space pattern of a predetermined dimension could not be resolved And the case was judged as X. [

&Lt; Evaluation of scum occurrence &

As a result of the resolution evaluation, in the case of ○ judgment, the resist pattern was observed by SEM, and the occurrence of scum was evaluated according to the following criteria.

?: No occurrence of scum was observed.

?: A small amount of scum was observed at the periphery of the resist pattern.

X: Occurrence of scum was observed on the entire surface of the resist pattern.

<Evaluation of Verticality of Side Wall of Resist Pattern on Substrate>

As a result of the resolution evaluation, in the case of ○ judgment, the cross section of the resist pattern was observed by SEM, and the perpendicularity of the side wall of the resist pattern to the substrate was evaluated according to the following criteria.

When the cross section of the resist pattern is observed, the maximum width Wmax and the minimum width Wmin of the width in the direction parallel to the surface direction of the substrate in the non-resist portion are measured to compare Wmax and Wmin . The criteria are as follows.

?: The value of Wmax-Wmin is 1 占 퐉 or less.

?: The value of Wmax-Wmin is more than 1 占 퐉 and not more than 2 占 퐉.

X: The value of Wmax-Wmin is more than 2 占 퐉.

<Evaluation of Peelability of Resist Pattern from Substrate>

A photosensitive film having a thickness of 5 탆 was formed in the same manner as in the evaluation of the resolution. The copper substrate provided with the photosensitive film was immersed in an aqueous solution of sodium hydroxide having a concentration of 1.0% by mass at 23 占 폚 for 3 minutes. After immersion, the substrate was washed with water. The surface of the washed substrate was observed with an optical microscope to determine the peelability according to the following criteria.

?: No residue of the resist (photosensitive film) was observed on the substrate.

?: Residues of the resist (photosensitive film) are observed on a part of the substrate.

X: Residues of the resist (photosensitive film) were observed on the entire surface of the substrate.

According to Table 1, (A) a novolak resin containing (A) a novolac resin containing a predetermined amount of (A1) novolak resin, or (A) In the case of a positive type photoresist composition containing the introduced (A1 ') novolac resin, even when the development is carried out using a basic aqueous solution having a low pH, in the case of observing the cross section of the resist pattern while suppressing occurrence of scum , It can be seen that a fine resist pattern can be formed in which the sidewall of the resist portion has a good shape perpendicular or substantially perpendicular to the substrate and is easily peeled off from the substrate.

According to Example 3, when the positive photoresist composition contains (C) a high boiling point compound, it is easy to form a resist pattern which is easy to inhibit scum formation and has a good shape.

Claims (13)

(A) a novolac resin, and (B) a photosensitive agent,
Wherein the novolak resin (A) comprises a novolac resin (A1) soluble in a basic aqueous solution having a pH of 12 and containing a unit derived from phenol,
The mass ratio of the novolac resin (A1) to the mass of the novolak resin (A) is more than 50% by mass,
Wherein the photosensitive agent (B) is a compound having a naphthoquinone diazide group. The method according to claim 1,
Wherein the novolac resin (A) further comprises a unit derived from an alkylphenol, which is insoluble in a basic aqueous solution having a pH of 13 but contains a novolac resin (A2) having solubility in a basic aqueous solution having a pH of more than 13, A positive photoresist composition. 3. The method according to claim 1 or 2,
Wherein the novolak resin (A1) consists only of a unit derived from phenol. 4. The method according to any one of claims 1 to 3,
Wherein in the part of the phenolic hydroxyl group of the novolac resin (A), the hydrogen atom in the phenolic hydroxyl group is substituted with a group containing a naphthoquinone diazide group. (A ') a novolac resin having a naphthoquinone diazide group,
Wherein the novolac resin (A ') is a resin obtained by (A) replacing a hydrogen atom in the phenolic hydroxyl group with a group containing a naphthoquinonediazide group in a part of the phenolic hydroxyl group of the novolak resin,
Wherein the novolak resin (A) comprises a novolac resin (A1) soluble in a basic aqueous solution having a pH of 12 and containing a unit derived from phenol,
Wherein the mass ratio of the mass of the novolac resin (A1) to the mass of the novolac resin (A) is more than 50 mass%. 6. The method of claim 5,
Wherein the novolac resin (A) further comprises a unit derived from an alkylphenol, which is insoluble in a basic aqueous solution having a pH of 13 but contains a novolac resin (A2) having solubility in a basic aqueous solution having a pH of more than 13, A positive photoresist composition. The method according to claim 5 or 6,
Wherein the novolak resin (A1) consists only of a unit derived from phenol. 8. The method according to any one of claims 1 to 7,
(S) &lt; / RTI &gt; solvent. 9. The method according to any one of claims 1 to 8,
(C) a high boiling point organic compound having a boiling point of 180 DEG C or higher at atmospheric pressure and being water-soluble. A photosensitive film-attached substrate comprising, on a substrate, a photosensitive film comprising the positive-working photoresist composition according to any one of claims 1 to 9. 10. A method of producing a photosensitive film comprising the steps of: selectively exposing a photosensitive film comprising the positive-working photoresist composition according to any one of claims 1 to 9,
And developing the exposed photosensitive film. 12. The method of claim 11,
Wherein the above phenomenon is carried out using a basic aqueous solution having a pH of 12 or less. 13. The method of claim 12,
Wherein the basic aqueous solution is an aqueous sodium carbonate solution having a concentration of 5 mass% or less.