WO2022059448A1 - Method for producing resist pattern, resist pattern and positive photosensitive resin composition for production of transparent multilayer member - Google Patents

Abstract

The present invention provides a method for producing a resist pattern, said method enabling the achievement of a fine resist pattern having high heat resistance, wherein a dilute weak alkaline developer solution is able to be used. The present invention specifically provides a method for producing a resist pattern, said method comprising: a coating film formation step wherein a coating film is formed on a base material; a light exposure step wherein the coating film is exposed to light; and a development step wherein the coating film after the light exposure step is developed by means of a dilute weak alkaline developer solution. With respect to this method for producing a resist pattern, the coating film contains: a novolac-type phenolic resin (A) which uses, as essential reactant materials, an aldehyde compound and a phenolic hydroxyl group-containing compound that contains an aromatic compound (a) represented by general formula (1), wherein 80% by mole or more of constituent units derived from the phenolic hydroxyl group-containing compound are constituent units (a) derived from the aromatic compound (a); and a sensitizing agent (B).

Description

A method for manufacturing a resist pattern, a resist pattern, and a positive photosensitive resin composition for manufacturing a transparent laminated member.

The present invention relates to a method for manufacturing a resist pattern, a resist pattern, and a positive photosensitive resin composition for manufacturing a transparent laminated member.

A positive type containing an alkali-soluble resin and a photosensitive agent such as a 1,2-naphthoquinonediazide compound as a resin composition used for manufacturing semiconductors such as ICs and LSIs, manufacturing display devices such as LCDs, and manufacturing original printing plates. Photosensitive resin compositions are known. In the field of photoresists, a wide variety of resist pattern forming methods that are subdivided according to applications and functions are being developed one after another, and along with this, the required performance for resist resin materials is becoming more sophisticated and diversified. ..

An aqueous solution of tetramethylammonium hydroxide is widely used as a developing solution used for developing a coating film formed by applying a positive photosensitive resin composition to a substrate, and the tetramethylammonium hydroxide is toxic. Is high and the environmental load is large. Therefore, a positive photosensitive resin composition capable of obtaining a coating film that can be developed with a weak alkaline developer having a small environmental load such as an aqueous solution of sodium carbonate or an aqueous solution of sodium hydrogen carbonate has been studied (for example, Patent Document 1).

Further, as a touch panel detection element or the like including a display element such as a liquid crystal display, a transparent laminated member having an electrode pattern made of a transparent conductive film on a transparent substrate is used. Generally, a glass substrate is used as a transparent substrate, and an ITO (Indium Tin Oxide) thin film or the like is used as a transparent conductive film.

As a method of forming an electrode pattern on a transparent substrate, a coating film made of a positive photosensitive resin composition is formed on a transparent conductive film formed on the transparent substrate, and the coating film is exposed from above via a mask. A method is known in which a coating film on an exposed portion is removed by developing with an alkaline developer, an exposed transparent conductive film is etched, and the remaining coating film is removed.

Due to the depletion of indium, it is being considered to substitute ITO, which is a transparent conductive film used for an electrode, with ZnO or a ZnO containing a metal as an additive (hereinafter referred to as "ZnO-based film"). However, since the ZnO-based film is damaged by strong alkali, it is known that a practical electrode pattern cannot be produced by using a strong alkali developer for development. Therefore, the development of a positive photosensitive resin composition capable of forming a coating film that can be developed with a weak alkaline developer such as an aqueous solution of sodium carbonate or an aqueous solution of sodium hydrogen carbonate, in which the ZnO-based film is not easily damaged, is also being considered. (For example, Patent Document 2).

Japanese Unexamined Patent Publication No. 2001-114853 Japanese Unexamined Patent Publication No. 2008-112134

In recent years, since the pattern tends to be finer due to the high integration of semiconductors and the like, a coating film made of a positive photosensitive resin composition is required to have higher sensitivity. The coating film made of the positive photosensitive resin composition has a problem that the sensitivity corresponding to the miniaturization of the pattern cannot be obtained.

Further, since the resin contained in the positive photosensitive resin composition described in Patent Document 2 has poor affinity with the photosensitive agent, the coating film made of the positive photosensitive resin composition described in Patent Document 2 has a poor affinity with the photosensitive agent. There is a problem that it is not suitable for drawing fine patterns.

Further, the coating film made of the positive photosensitive resin composition described in Patent Document 1 and Patent Document 2 has a problem that a sufficient dissolution rate cannot be obtained in development with a weak alkaline developer.

Further, since various heat treatments are applied in the manufacturing process of semiconductors and the like, high heat resistance is required for the resist pattern, but the positive photosensitive resin composition described in Patent Document 1 has sufficient heat resistance. There is a problem that it is not possible to obtain a resist pattern having the above.

As described above, a positive photosensitive resin composition and a weak photosensitive resin composition, which have excellent solubility in a weak alkaline developer, are suitable for drawing fine patterns, and can obtain a resist pattern having high heat resistance. There is a need to develop a method for producing a resist pattern that can be used with an alkaline developer.

An object of the present invention is to provide a method for producing a resist pattern, which can use a weak alkaline developer and can obtain a fine resist pattern having high heat resistance.

The present invention also provides a positive photosensitive resin composition for manufacturing a transparent laminated member capable of obtaining a fine resist pattern having high heat resistance while having excellent solubility in a weak alkaline developer. Is the subject.

The present inventors have conducted diligent studies in order to solve the above problems. As a result, by using a specific novolak-type phenol resin for the production of the resist pattern, it is possible to develop with a weak alkaline developer, further, it is possible to draw a fine resist pattern, and the positive-type photosensitive is also possible. It has been found that a resist pattern made of a sex resin composition has high heat resistance.

Furthermore, the present inventors obtain a coating film capable of developing with a dilute weak alkaline developer having a lower alkaline strength than the weak alkaline developer conventionally studied by the specific novolak type phenol resin. We found that it is possible to further suppress damage to ZnO-based films.

That is, the present invention
A coating film forming process for forming a coating film on a substrate,
A method for producing a resist pattern, comprising an exposure step of exposing the coating film and a developing step of developing the coating film with a dilute and weak alkaline developer after the exposure step.
The coating film is derived from the phenolic hydroxyl group-containing compound using the phenolic hydroxyl group-containing compound containing the aromatic compound (a) represented by the following general formula (1) and the aldehyde compound as essential reaction raw materials. This is a method for producing a resist pattern, which contains a novolak-type phenol resin (A) and a photosensitizer (B) in which 80 mol% or more of the constituent units are the constituent units (a) derived from the aromatic compound (a).

[In the general formula (1), R ¹ and R ² independently represent an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group or a halogen atom. m, n and p each independently represent an integer of 0 to 4. When there are a plurality of R ¹ , the plurality of R ^1s may be the same or different from each other. When there are a plurality of R ^2s , the plurality of R ^2s may be the same or different from each other. R ³ represents a structural moiety having one or more substituents selected from an alkoxy group, a halogen group and a hydroxyl group on a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a hydrocarbon group. ^R4 represents a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group or a halogen atom. When there are a plurality of ^R4s , the plurality of ^R4s may be the same or different from each other. ]

Further, the present invention is a resist pattern manufactured by the method for manufacturing a resist pattern.

Further, the present invention
An essential reaction raw material is a phenolic hydroxyl group-containing compound containing the aromatic compound (a) represented by the following general formula (1) and an aldehyde compound, and 80 mol of a constituent unit derived from the phenolic hydroxyl group-containing compound is used. Positive type photosensitive for manufacturing a transparent laminated member containing a novolak type phenol resin (A), a photosensitizer (B), and a solvent (C) in which% or more is a structural unit (a) derived from the aromatic compound (a). It is a phenolic resin composition.

[In the general formula (1), R ¹ and R ² independently represent an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group or a halogen atom. m, n and p each independently represent an integer of 0 to 4. When there are a plurality of R ¹ , the plurality of R ^1s may be the same or different from each other. When there are a plurality of R ^2s , the plurality of R ^2s may be the same or different from each other. R ³ represents a structural moiety having one or more substituents selected from an alkoxy group, a halogen group and a hydroxyl group on a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a hydrocarbon group. ^R4 represents a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group or a halogen atom. When there are a plurality of ^R4s , the plurality of ^R4s may be the same or different from each other. ]

According to the present invention, it is possible to provide a method for producing a resist pattern, which can obtain a fine resist pattern having high heat resistance by using a dilute and weak alkaline developer for development.

The present invention also provides a positive photosensitive resin composition for manufacturing a transparent laminated member capable of obtaining a coating film having excellent solubility in a dilute and weak alkaline developer and a fine resist pattern having high heat resistance. can do.

GPC chart of the aromatic compound (a) obtained in Synthesis Example 1 ¹³ C-NMR chart of aromatic compound (a) obtained in Synthesis Example 1 GPC chart of novolak type phenol resin (A-1) obtained in Synthesis Example 2 GPC chart of novolak type phenol resin (A-2) obtained in Synthesis Example 3

The method for producing a resist pattern according to an embodiment of the present invention is as follows.
A coating film forming process for forming a coating film on a substrate,
A method for producing a resist pattern, comprising an exposure step of exposing the coating film and a developing step of developing the coating film with a dilute and weak alkaline developer after the exposure step.
The coating film is derived from the phenolic hydroxyl group-containing compound using the phenolic hydroxyl group-containing compound containing the aromatic compound (a) represented by the following general formula (1) and the aldehyde compound as essential reaction raw materials. 80 mol% or more of the structural unit contains the novolak type phenol resin (A), which is the structural unit (a) derived from the aromatic compound (a), and the photosensitizer (B).

[In the general formula (1), R ¹ and R ² independently represent an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group or a halogen atom. m, n and p each independently represent an integer of 0 to 4. When there are a plurality of R ¹ , the plurality of R ^1s may be the same or different from each other. When there are a plurality of R ^2s , the plurality of R ^2s may be the same or different from each other. R ³ represents a structural moiety having one or more substituents selected from an alkoxy group, a halogen group and a hydroxyl group on a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a hydrocarbon group. ^R4 represents a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group or a halogen atom. When there are a plurality of ^R4s , the plurality of ^R4s may be the same or different from each other. ]

According to the method for producing a resist pattern of the present embodiment, a dilute and weak alkaline developer can be used for development, and a fine resist pattern having high heat resistance can be obtained. The reason why the method for producing the resist pattern of the present embodiment exerts such an effect is not clear, but it is considered as follows.

Since the novolak-type phenol resin (A) has a triarylmethane structure and contains an aromatic ring at a high density, the resist pattern containing the novolak-type phenol resin (A) has very high heat resistance. Further, in the triarylmethane structure of the general formula (1), the two hydroxy groups and the carboxy group are substituted with different aromatic rings, and a strong hydrogen bond is not formed. As a result, the novolak-type phenol resin (A) retains good proton dissociation property and has excellent affinity with the photosensitizer. Therefore, the resist pattern containing the novolak-type phenol resin (A) is used as an exposed portion in photolithography. It has a high contrast between the and unexposed areas and is suitable for drawing fine patterns. Further, since the novolak-type phenol resin (A) maintains good proton dissociation property, the coating film containing the novolak-type phenol resin (A) is excellently dissolved in a dilute and weak alkaline developer in the exposed portion. Show sex. From the above, according to the method for producing a resist pattern of the present embodiment using the positive photosensitive resin composition containing the novolak type phenol resin (A), a dilute and weak alkaline developer can be used for development, which is high. It is considered that a fine resist pattern having heat resistance can be obtained.

The coating film forming step is a step of forming a coating film on the base material. The coating film is derived from the phenolic hydroxyl group-containing compound using the phenolic hydroxyl group-containing compound containing the aromatic compound (a) represented by the general formula (1) and the aldehyde compound as essential reaction raw materials. 80 mol% or more of the structural unit contains the novolak type phenol resin (A), which is the structural unit (a) derived from the aromatic compound (a), and the photosensitizer (B).

The novolak-type phenol resin (A) has the above-mentioned general formula (1) from the viewpoint of obtaining a resist pattern having high heat resistance, which is suitable for drawing a fine pattern while having excellent solubility in a dilute weak alkaline developer. ), The aromatic compound (a) and the aldehyde compound are essential reaction raw materials, and 80 mol% or more of the phenolic hydroxyl group-containing compound constituting the novolak structure is the aromatic compound (a). It is a feature.

In the general formula (1), the aliphatic hydrocarbon group having 1 to 9 carbon atoms of R ¹ , R ² , R ³ , R ⁴ and R ⁵ includes a methyl group, an ethyl group, a propyl group and an isopropyl group. Examples thereof include an alkyl group having 1 to 9 carbon atoms and a cycloalkyl group having 3 to 9 carbon atoms such as a butyl group, a t-butyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group and a nonyl group.

In the general formula (1), examples of the alkoxy group of R ¹ , R ² and R ⁴ include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a cyclohexyloxy group and the like. ..

In the general formula (1), examples of the aryl group of R ¹ and R ² include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group and the like.

In the general formula (1), examples of the aralkyl group of R ¹ and R ² include a benzyl group, a phenylethyl group, a phenylpropyl group, a naphthylmethyl group and the like.

In the general formula (1), examples of the halogen atom of R ¹ , R ² and R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

In the general formula (1), the "structural moiety having one or more substituents selected from an alkoxy group, a halogen group and a hydroxyl group ^on the hydrocarbon group" of R3 includes an alkyl halide group and an aryl halide group. Examples thereof include an alkoxyalkoxy group such as a 2-methoxyethoxy group and a 2-ethoxyethoxy group, and an alkylalkoxy group substituted with a hydroxy group.

In the general formula (1), m and n are preferably integers of 2 or 3, respectively. When m and n are 2 respectively, it is preferable that the two ^R1s and the ^two R2s are independently alkyl groups having 1 to 3 carbon atoms. At this time, it is preferable that the two ^R1s and the ^two R2s are bonded to the 2,5-positions of the phenolic hydroxyl groups, respectively.

In the general formula (1), R ³ is preferably a hydrogen atom.

In the general formula (1), p is preferably an integer of 0, 1 or 2.

As the aromatic compound (a), a compound having the same structure may be used alone, or a plurality of compounds having different molecular structures may be used.

The novolak-type phenol resin (A) can be produced, for example, by the method for producing the novolak-type phenol resin (A) having the following steps 1 to 3.
(Step 1)
The phenol compound (a1) and the aromatic aldehyde or aromatic ketone (a2) having a carboxy group are heated in the range of 60 to 140 ° C. in the presence of an acid catalyst, if necessary, using a solvent, and polycondensed. Thereby, the aromatic compound (a) is obtained.
(Step 2)
The aromatic compound (a) obtained in the step 1 is isolated from the reaction solution.
(Step 3)
The aromatic compound (a) isolated in the step 2 and the aldehyde compound are used as essential reaction raw materials, and these are used in the presence of an acid catalyst and, if necessary, a solvent in the range of 60 to 140 ° C. The novolak type phenol resin (A) is obtained by heating and polycondensing.

In addition to the phenol, the phenol compound (a1) does not have one substituent such as an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group or a halogen atom on the aromatic ring of the phenol. Examples thereof include compounds having a plurality of compounds. Specific examples of these substituents include those exemplified as R ¹ and R ² in the general formula (1). Above all, since it is a novolak type phenol resin (A) having further excellent solubility in a dilute and weak alkaline developer, it is preferably an alkylphenol having two or three alkyl groups having 1 to 3 carbon atoms. Specific examples of the alkylphenol include monoalkylphenols such as o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, and p-ethylphenol; 2,5-xylenol and 3,5-xylenol. , 3,4-Xylenol, 2,4-xylenol, dialkylphenols such as 2,6-xylenol; trialkylphenols such as 2,3,5-trimethylphenol, 2,3,6-trimethylphenol and the like. Among these, dialkylphenol is preferable, and 2,5-xylenol and 2,6-xylenol are more preferable. The phenol compound (a1) may be used alone or in combination of two or more.

Among the aromatic aldehydes or aromatic ketones (a2) having a carboxy group, specific examples of the aromatic aldehyde include a compound having a formyl group on a benzene ring such as benzene, phenol and resorcin, and a formyl group. Examples thereof include compounds having an alkyl group, an alkoxy group, a halogen atom and the like. Specific examples thereof include 4-formylbenzoic acid, 2-formylbenzoic acid, 3-formylbenzoic acid and the like. Of these, 4-formylbenzoic acid is preferred. These may be used alone or in combination of two or more.

Among the aromatic aldehydes or aromatic ketones (a2) having a carboxy group, specific examples of the aromatic ketone include, for example, 2-acetylbenzoic acid, 3-acetylbenzoic acid, 4-acetylbenzoic acid, and 2-. Methyl acetylbenzoate, ethyl 2-acetylbenzoate, propyl 2-acetylbenzoate, isopropyl 2-acetylbenzoate, butyl 2-acetylbenzoate, isobutyl 2-acetylbenzoate, tertiary butyl 2-acetylbenzoate, 2 -Cyclohexyl acetylbenzoate, tertiary octyl 2-acetylbenzoate and the like can be mentioned. Of these, 2-acetylbenzoic acid and 4-acetylbenzoic acid are preferable. These may be used alone or in combination of two or more.

Among the aromatic aldehydes or aromatic ketones (a2) having a carboxy group, novolak-type phenol having excellent reactivity with the phenol compound (a1) and further excellent solubility in a dilute weak alkaline developing solution. Since it becomes the resin (A), it is preferable to use an aromatic aldehyde, and 4-formylbenzoic acid is particularly preferable.

As the aldehyde compound, an aliphatic aldehyde, an aromatic aldehyde or the like can be used, but the novolak type phenol resin (A) having further excellent solubility in a dilute weak alkaline developer is preferable. ..

Specific examples of the aliphatic aldehydes include formaldehyde, paraformaldehyde, 1,3,5-trioxane, acetaldehyde, propionaldehyde, tetraoxymethylene, polyoxymethylene, chloral, hexamethylenetetramine, glioxal, n-butyraldehyde, and the like. Examples thereof include caproaldehyde, allyl aldehyde, croton aldehyde, achlorein and the like. Among these, one or more selected from formaldehyde and paraformaldehyde is preferable, and formaldehyde is more preferable. The aliphatic aldehydes may be used alone or in combination of two or more. When formaldehyde and an aliphatic aldehyde other than formaldehyde are used as the aliphatic aldehydes, the amount of the aliphatic aldehyde other than formaldehyde shall be in the range of 0.05 to 1 mol with respect to 1 mol of formaldehyde. Is preferable.

The novolak-type phenol resin (A) uses the aromatic compound (a) and the aldehyde compound as essential reaction raw materials, but components other than these may be contained in the reaction raw materials. Specific examples thereof include phenol compounds other than the aromatic compound (a).

Since the effect of the present invention is sufficiently exhibited, 80 mol% or more of the phenolic hydroxyl group-containing compound constituting the novolak structure of the novolak type phenol resin (A) is the aromatic compound (a). Is preferable, and 90 mol% or more is more preferable. Further, it is preferable that 80 mol% or more of the structural unit derived from the aldehyde compound of the novolak type phenol resin (A) is the structural unit (b) derived from the aliphatic aldehydes, and 90% or more. Is more preferable.

Examples of the acid catalyst that can be used in the steps 1 and 3 include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenol sulfonic acid, paratoluene sulfonic acid, zinc acetate, manganese acetate and the like. These acid catalysts may be used alone or in combination of two or more. Among these acid catalysts, sulfuric acid and p-toluenesulfonic acid are preferable in the step 1, and sulfuric acid, oxalic acid and zinc acetate are preferable in the step 3 from the viewpoint of excellent activity. The acid catalyst may be added before the reaction or during the reaction.

Examples of the solvent that can be used in the steps 1 and 3 as needed include carboxylic acid compounds such as formic acid, acetic acid, propionic acid, butyric acid, and valeric acid; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and the like. Glycol ether compounds such as ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, and ethylene glycol monophenyl ether; 1,3-dioxane, 1,4-dioxane, etc. Cyclic ether compounds; glycol ester compounds such as ethylene glycol acetate; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene can be mentioned. These solvents may be used alone or in combination of two or more. Among these solvents, acetic acid is preferable because the obtained compound is excellent in solubility.

The charging ratio [(a1) / (a2)] of the phenol compound (a1) to the aromatic aldehyde or aromatic ketone (a2) having a carboxy group in the step 1 is the unreacted phenol compound (a1). The molar ratio is preferably in the range of 1 / 0.8 to 1 / 0.2, preferably 1 / 0.6 to 1/0, because it is excellent in removability and the yield and purity of the obtained aromatic compound (a). The range of 0.4 is more preferable.

As a method for isolating the aromatic compound (a) from the reaction solution in the step 2, for example, a precipitate obtained by putting the reaction solution into a poor solvent (S1) in which the reaction product is insoluble or sparingly soluble. A method is to separate the product by filtration, dissolve the reaction product in a solvent (S2) that is also compatible with the poor solvent (S1), and then put the reaction product into the poor solvent (S1) again to filter out the resulting precipitate. Can be mentioned. Examples of the poor solvent (S1) used in this case include water; monoalcohols such as methanol, ethanol and propanol; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane and cyclohexane; toluene and xylene. Such as aromatic hydrocarbons. Among these poor solvents (S1), water and methanol are preferable because the acid catalyst can be efficiently removed at the same time.

Examples of the solvent (S2) include monoalcohols such as methanol, ethanol and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol and 1,5-pentanediol. , 1,6-Hexanediol, 1,7-Heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin and other polyols; 2-ethoxyethanol, ethylene glycol Glycol ethers such as monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethylmethyl ether, ethylene glycol monophenyl ether; 1,3- Cyclic ethers such as dioxane and 1,4-dioxane; glycol esters such as ethylene glycol acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone can be mentioned. When water is used as the poor solvent (S1), acetone is preferable as the (S2). The poor solvent (S1) and the solvent (S2) may be used alone or in combination of two or more.

When aromatic hydrocarbons such as toluene and xylene are used as the solvent in the steps 1 and 3, the aromatic compound (a) produced by the reaction dissolves in the solvent when heated at 80 ° C. or higher. Therefore, since the crystal of the aromatic compound (a) is precipitated by cooling as it is, the aromatic compound (a) can be isolated by filtering it. In this case, the poor solvent (S)
It is not necessary to use 1) and the solvent (S2).

The aromatic compound (a) can be obtained by the isolation method of the step 2.

The purity of the aromatic compound (a) is preferably 90% or more, more preferably 94% or more, and 98% or more, which is the purity calculated from the gel permeation chromatography (GPC) chart. It is particularly preferable to have. The purity of the aromatic compound (a) can be determined from the area ratio of the chart diagram of GPC, and is measured under the measurement conditions described later.

The charging ratio of the aromatic compound (a) to the aldehyde compound in the step 3 [the aromatic compound (a) / the aldehyde compound] can suppress excessive high molecular weight (gelling) and is a phenol for resist. Since a resin having an appropriate molecular weight can be obtained, the molar ratio is preferably in the range of 1 / 1.2 to 1 / 0.5, more preferably in the range of 1 / 0.9 to 1 / 0.6. When other phenol compounds other than the aromatic compound (a) are used, [(total number of moles of phenolic hydroxyl group-containing compound constituting the novolak type phenol resin (A)) / (novolak type phenol). The total number of moles of the aldehyde compound constituting the resin (A))] is preferably in the range of 1 / 1.2 to 1 / 0.5, and is preferably in the range of 1 / 0.9 to 1 / 0.6. It is more preferable to have.

The weight average molecular weight (Mw) of the novolak-type phenol resin (A) is preferably in the range of 2,000 to 20,000, more preferably in the range of 2,000 to 10,000. In the present specification, the weight average molecular weight (Mw) of the (A) novolak type phenol resin was measured by gel permeation chromatography (hereinafter abbreviated as “GPC”) under the measurement conditions described in Examples. It is a thing.

The content of the novolak-type phenol resin (A) in the coating film is preferably 5% by mass or more, more preferably 10% by mass or more, particularly, because good sensitivity can be obtained and a desired pattern can be obtained. It is preferably in the range of 50% by mass or more, preferably 95% by mass or less, and more preferably 80% by mass or less.

The photosensitive agent (B) is, for example, a compound having a quinonediazide group. Specific examples of the compound having a quinonediazide group include an ester compound or an amidate of an aromatic (poly) hydroxy compound and a sulfonic acid compound having a quinonediazide group. The ester compound also means to include a partial ester compound, and the amidate means to include a partial amidate.

Specific examples of the sulfonic acid compound having a quinone diazide group include naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, orthoanthraquinone diazidosulfonic acid, 1,2-. Examples thereof include naphthoquinone-2-diazide-5-sulfonic acid. As a specific example of the sulfonic acid compound having a quinonediazide group, a halide further substituted with a halogen can also be used.

Examples of the aromatic (poly) hydroxy compound 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, Polyhydroxybenzophenone compounds such as 4', 5', 6-hexahydroxybenzophenone, 2,3,3', 4,4', 5'-hexahydroxybenzophenone; bis (2,4-dihydroxyphenyl) methane, bis ( 2,3,4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2', 4) '-Dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (2', 3', 4'-trihydroxyphenyl) propane, 4,4'-{1- [4- [4- [2- (4-Hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol, 4,4'-[1- [4- [1- (4-hydroxyphenyl) -1methylethyl] phenyl] ethylidene] bisphenol , 3,3'-dimethyl- {1- [4- [2- (3-methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol and other bis [(poly) hydroxyphenyl] alkane compounds; Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-Hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethyl) Phenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, etc. Tris (hydroxyphenyl) methane compound or its methyl substituent; 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-hydroxyphenyl Methan, 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, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane, etc. Examples thereof include a bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methane compound or a methyl substituent thereof. These may be used alone or in combination of two or more.

The content of the photosensitive agent (B) in the coating film is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 10% by mass or more, because good sensitivity can be obtained and a desired pattern can be obtained. The range is 50% by mass or less, more preferably 30% by mass or less.

The coating film may contain other phenolic hydroxyl group-containing compounds in addition to the novolak-type phenol resin (A) as long as the effects of the present invention are not impaired. In that case, the ratio of the novolak-type phenol resin (A) to the total of the novolak-type phenol resin (A) and other phenolic hydroxyl group-containing compounds is preferably 50% by mass or more, preferably 80% by mass or more. It is more preferable, and it is particularly preferable that it is 90% by mass or more.

Examples of the other phenolic hydroxyl group-containing compound include phenolic hydroxyl group-containing compounds such as phenol, cresol, naphthol, biphenol, bisphenol, and triphenylmethane, and phenolic resins such as phenol novolac resin, cresol novolak resin, and bisphenol novolak. Can be mentioned. Each of these may be used alone or in combination of two or more.

The base material is an object for photolithography. Examples of the base material include a silicon substrate, a silicon carbide substrate, and a gallium nitride substrate. However, since the method for producing a resist pattern in the present embodiment uses a dilute and weak alkaline developer, the base material contains zinc oxide. Even in the case of a transparent conductive film, a fine resist pattern having high heat resistance can be obtained.

As a method for forming a coating film on the substrate, any method used in the field of photolithography can be used without limitation. For example, the novolak type phenol resin (A), the photosensitive agent (B), and the solvent ( A positive photosensitive resin composition for manufacturing a transparent laminated member (hereinafter, also simply referred to as “positive photosensitive resin composition”) containing C) is applied to the substrate, and the temperature condition is 60 to 150 ° C. There is a method of prebaking.

As a method of applying the positive photosensitive resin composition to the substrate, any method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor blade coating and the like may be used.

The content of the novolak-type phenol resin (A) in the positive-type photosensitive resin composition is preferably in the resin solid content (in the components excluding the solvent (C) of the positive-type photosensitive resin composition). It is in the range of 5% by mass or more, more preferably 10% by mass or more, particularly preferably 50% by mass or more, preferably 95% by mass or less, and more preferably 80% by mass or less.

The content of the photosensitive agent (B) in the positive photosensitive resin composition is preferably in the resin solid content (in the components excluding the solvent (C) of the positive photosensitive resin composition). The range is from 5% by mass or more, more preferably 10% by mass or more, preferably 50% by mass or less, and more preferably 30% by mass or less.

Examples of the solvent (C) include polar aprotonic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide and dimethylsulfoxide, tetrahydrofuran, dioxane and propylene. Ethers such as glycol monomethyl ether and propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone and diisobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxy Examples thereof include esters such as butyl acetate, alcohols such as ethyl lactate, methyl lactate, diacetone alcohol and 3-methyl-3-methoxybutanol, and aromatic hydrocarbons such as toluene and xylene. These solvents may be used alone or in combination of two or more.

The content of the solvent (C) in the positive photosensitive resin composition sufficiently increases the fluidity of the positive photosensitive resin composition, and a uniform coating film can be obtained by a coating method such as a spin coating method. Therefore, the solid content concentration in the positive photosensitive resin composition is preferably 5% by mass or more, and preferably 65% by mass or less.

The positive photosensitive resin composition may contain other phenolic hydroxyl group-containing compounds in addition to the novolak type phenol resin (A) as long as the effects of the present invention are not impaired. In that case, the ratio of the novolak-type phenol resin (A) to the total of the novolak-type phenol resin (A) and other phenolic hydroxyl group-containing compounds is preferably 50% by mass or more, preferably 80% by mass or more. It is more preferable, and it is particularly preferable that it is 90% by mass or more.

Examples of the other phenolic hydroxyl group-containing compound include phenolic hydroxyl group-containing compounds such as phenol, cresol, naphthol, biphenol, bisphenol, and triphenylmethane, and phenolic resins such as phenol novolac resin, cresol novolak resin, and bisphenol novolak. Can be mentioned. Each of these may be used alone or in combination of two or more.

The positive photosensitive resin composition contains the novolak type phenol resin (A), the photosensitive agent (B), the solvent (C), and various additives as long as the effects of the present invention are not impaired. It doesn't matter if you do. Examples of various additives include fillers, curing agents capable of reacting with the novolak-type phenol resin (A), curing accelerators, pigments, surfactants such as leveling agents, adhesion improvers, dissolution accelerators and the like. ..

Examples of the curing agent include urea resin, melamine resin, furan resin, xylene resin, epoxy resin, unsaturated polyester resin, thermosetting polyimide, thermosetting polyamide-imide and the like. As the curing accelerator, a known and commonly used agent capable of accelerating the curing reaction can be used depending on the curing agent used. When these curing agents and curing accelerators are used, a resist pattern is formed by a method described later and then heated to obtain a resist film having higher heat resistance.

In the positive photosensitive resin composition, the novolak type phenol resin (A), the photosensitive agent (B), the solvent (C), and various additives added as needed are added by a usual method. It can be prepared by stirring and mixing to obtain a uniform liquid.

Further, when a solid material such as a filler or a pigment is blended with the positive photosensitive resin composition, it is preferable to disperse and mix using a disperser such as a dissolver, a homogenizer, or a three-roll mill. Further, in order to remove coarse particles and impurities, the composition can be filtered using a mesh filter, a membrane filter or the like.

The exposure step is a step of exposing the coating film through a mask on which a pattern is drawn. Examples of the light source for exposing the coating film include infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams. Among these light sources, ultraviolet light is preferable, and g-line (wavelength 436 nm) and i-line (wavelength 365 nm) of a high-pressure mercury lamp are preferable.

The developing step is a step of developing the coating film after the exposure step with a dilute and weak alkaline developer. In the developing step, a resist pattern is formed by developing the coating film after the exposure step with a dilute and weak alkaline developer. Since the novolak-type phenol resin (A) contained in the coating film has a characteristic of being excellent in alkali solubility, sufficient development is possible even when a dilute and weak alkaline developer is used. At the same time, since the novolak type phenol resin (A) has excellent compatibility with the photosensitizer, the alkali resistance in the unexposed area is very high, and as a result, the contrast between the exposed area and the unexposed area in photolithography is high. It is possible to draw high and fine patterns. Further, by using a dilute and weak alkaline developer in the developing step, the resist pattern can be developed while suppressing damage to the ZnO-based film.

In the present specification, the dilute weak alkaline developer is 0.1 of an inorganic salt of an acid having a pKa in the range of 6.0 to 12.0 in _H2O at 23 ° C. It means ~ 10% by mass aqueous solution. Examples of the inorganic acid include sodium carbonate and sodium hydrogen carbonate. The pH of the dilute and weak alkaline developer used in the developing step is preferably in the range of 8.0 or more and 12.0 or less.

When a mixed solution of an aqueous solution of sodium carbonate and an aqueous solution of sodium hydrogen carbonate is used as the dilute weak alkaline developer, the mixing ratio of the two is not particularly limited and can be used in any ratio. Above all, since a particularly high contrast can be obtained, the mass ratio of the two [(sodium carbonate aqueous solution) / (sodium hydrogen carbonate aqueous solution) is preferably in the range of 80/20 to 20/80, and 80/20 to 60 /. It is more preferably in the range of 40.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

<GPC measurement conditions>
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation
Column: "Shodex KF802" manufactured by Showa Denko KK (8.0 mm Ф x 300 mm)
+ "Shodex KF802" manufactured by Showa Denko KK (8.0 mm Ф x 300 mm)
+ "Shodex KF803" manufactured by Showa Denko KK (8.0 mm Ф x 300 mm)
+ "Shodex KF804" manufactured by Showa Denko KK (8.0 mm Ф x 300 mm)
Column temperature: 40 ° C
Detector: RI (Differential Refractometer)
Data processing: "GPC-8020 Model II Version 4.30" manufactured by Tosoh Corporation
Developing solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample: Tetrahydrofuran solution of 0.5% by mass in terms of resin solid content filtered through a microfilter (100 μl)
Standard sample: The following monodisperse polystyrene

(Standard sample: monodisperse polystyrene)
"A-500" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation

< ^{1 1} H-NMR measurement conditions>
Equipment: JNM-ECA500 manufactured by JEOL Ltd.
Measurement mode: ^SGNNE (1H complete decoupling method for NOE elimination)
Solvent: Deuterated dimethyl sulfoxide Pulse angle: 45 ° pulse Sample concentration: 30% by mass
Accumulation number: 10,000 times

In this example, ¹³ C-NMR was measured under the following conditions.

< ¹³ C-NMR measurement conditions>
Equipment: JNM-ECA500 manufactured by JEOL Ltd.
Measurement mode: Decoupling with reverse gate Solvent: Deuterated dimethyl sulfoxide Pulse angle: 30 ° pulse Sample concentration: 30% by mass
Number of integrations: 4000 times Criteria for chemical shift: Peak of dimethyl sulfoxide: 39.5 ppm

[Synthesis Example 1: Synthesis of Aromatic Compound (a)]
2,5-Xylenol 293.2 g (2.4 mol) and 4-formylbenzoic acid 150 g (1 mol) were charged into a 2000 ml 4-neck flask provided with a cooling tube and dissolved in 500 ml of acetic acid. After adding 5 ml of sulfuric acid while cooling in an ice bath, the mixture was heated at 100 ° C. for 2 hours with a mantle heater and stirred to react. After the reaction, the obtained solution was reprecipitated with water to obtain a crude product. The crude product was redissolved in acetone and further subjected to a reprecipitation operation with water, and then the obtained product was filtered off and vacuum dried to obtain 292 g of a pale pink crystalline aromatic compound (a). The GPC purity was 95.3%, and it was confirmed by ¹ H-NMR that it was the target compound. The GPC chart of the obtained aromatic compound (a) is shown in FIG. 1, and the ¹³ C-NMR chart is shown in FIG.

[Synthesis Example 2: Synthesis of Novolac-type Phenolic Resin (A-1)]
188 g of the aromatic compound (a) synthesized in Synthesis Example 1 and 16 g of 92% paraformaldehyde were charged into a 1000 ml 4-neck flask provided with a cooling tube and dissolved in 500 ml of acetic acid. After adding 10 ml of sulfuric acid while cooling in an ice bath, the temperature was raised to 80 ° C. in an oil bath, and then heating and stirring were continued for 4 hours for reaction. After the reaction, the obtained solution was reprecipitated with water to obtain a crude product. The crude product was redissolved in acetone and further subjected to a reprecipitation operation with water, and then the obtained product was filtered off and vacuum dried to obtain 182 g of an orange powder novolak type phenol resin (A-1). .. The GPC of the novolak type phenol resin (A-1) had a number average molecular weight (Mn) = 3946, a weight average molecular weight (Mw) = 8504, and a polydispersity (Mw / Mn) = 2.16. The GPC chart is shown in FIG.

[Synthesis Example 3: Synthesis of Novolac Phenolic Resin (A-2)]
178 g of novolak type phenol resin (A-2) powder was obtained in the same manner as in Synthesis Example 2 except that 92% paraformaldehyde was changed to 12.8 g. The GPC of the novolak type phenol resin (A-2) had a number average molecular weight (Mn) = 2872, a weight average molecular weight (Mw) = 4920, and a polydispersity (Mw / Mn) = 1.73. The GPC chart is shown in FIG.

[Comparative Synthesis Example 1: Synthesis of Novolac Phenolic Resin (A')]
A reactor equipped with a stirrer, a reflux condenser and a thermometer is charged with 108 g of o-cresol, 100 g of a glyoxylic acid aqueous solution (grioxylic acid content 40%), 140 parts of diethylene glycol dimethyl ether, and 2.2 g of p-toluenesulfonic acid, and stirred. The reaction was carried out at 100 ° C. below. Next, 108 g of o-cresol and 120 g of diethylene glycol dimethyl ether were added, 102.2 g of a formalin aqueous solution (formaldehyde content 37%) was added dropwise at 90 ° C., and the temperature was raised to 150 ° C. for 6 hours under reflux conditions. It was reacted. After completion of the reaction, the obtained solution was washed with water to remove p-toluenesulfonic acid, and then water was distilled off under reduced pressure to obtain 216 g of novolak-type phenol formaldehyde (A') powder.

<Evaluation of heat resistance of novolak type phenol resin>
20 g of each of the novolak-type phenolic resins (A-1), (A-2) and (A') powder was dissolved in 80 g of γ-butyrolactone, finely filtered with a 0.1 μm PTFE disc filter, and each of them was used. A novolak type phenol resin solution was obtained. Each of these was applied on a silicon wafer having a diameter of 5 inches with a spin coater and dried at 110 ° C. for 60 seconds to obtain a thin film having a thickness of about 1 μm. This thin film was scraped off and the glass transition temperature (hereinafter abbreviated as "Tg") was measured. The Tg is measured using a differential thermal scanning calorimeter (“Differential Thermal Scanning Calorimeter (DSC) Q100” manufactured by TA Instruments Co., Ltd.) under a nitrogen atmosphere in a temperature range of -100 to 200 ° C. The temperature was raised at a rate of 10 ° C./min. The evaluation results are shown in Table 1.

<Evaluation of alkali solubility of novolak type phenol resin>
The above-mentioned novolak-type phenolic resin (A-1), (A-2) and (A') γ-butyrolactone solutions obtained above were each applied on a silicon wafer having a diameter of 5 inches with a spin coater, and the temperature was 110 ° C. It was dried on a hot plate for 60 seconds to form a thin film having a thickness of about 1 μm. The obtained wafer with a coating film was immersed in various weak alkaline developers for 60 seconds, and then dried on a hot plate at 110 ° C. for 60 seconds. The film thickness before and after immersion in the developing solution was measured, and the value obtained by dividing the difference by 60 was evaluated as ADR (Å / s). The evaluation results are shown in Table 2. The contents of each ADR in Table 2 are as follows. The higher the value, the higher the alkali solubility.
-ADR1 (Å / s): Value when a developer (pH 12) consisting of 1 mass% sodium carbonate aqueous solution is used as a weak alkaline developer.-ADR2 (Å / s): 1 mass% as a weak alkaline developer. Value when a developer (pH 11), which is a mixture of an aqueous sodium carbonate solution and a 1% by mass sodium hydrogen carbonate solution at a mass ratio of 75/25, is used.-ADR3 (Å / s): 1% by mass carbonate as a weak alkaline developer. Value when a developer (pH 10), which is a mixture of an aqueous sodium solution and a 1 mass% sodium hydrogen carbonate solution at a mass ratio of 50/50, is used.-ADR4 (Å / s): 1 mass% sodium carbonate as a weak alkaline developer Value when a developer (pH 9), which is a mixture of an aqueous solution and a 1 mass% sodium hydrogen carbonate solution at a mass ratio of 25/75, is used. ・ ADR5 (Å / s): 1 mass% sodium hydrogen carbonate as a weak alkaline developer. Value when using a developer (pH 8) consisting of an aqueous solution

<Preparation of positive photosensitive resin composition>
20 g of novolak type phenol resin (A-1) powder and photosensitizer ("P-200" manufactured by Toyo Synthetic Industry Co., Ltd., 4,4'-[1- [4- [1- (4-hydroxyphenyl)- 1 Methylethyl] Phenyl] Echilidene] A condensate of 1 mol of bisphenol and 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride) was dissolved in 75 g of γ-butyrolactone to form a positive photosensitive resin. I got the thing (1). Hereinafter, the types of the novolak type phenol resin and the photosensitive agent were changed as shown in Table 3 below, and the positive type photosensitive resin compositions (2) to (5) were obtained by the same method.

* In the table, "P-200" refers to "P-200" manufactured by Toyo Gosei Co., Ltd. (4,4'-[1- [4- [1- (4-hydroxyphenyl) -1 methylethyl] phenyl. ] Ethylidene] Condensate of 1 mol of bisphenol and 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride)
* In the table, "TPPA (4) -200" refers to "TPPA (4) -200" manufactured by Toyo Gosei Co., Ltd.
* "MS-280" in the table refers to "MS-280" manufactured by Toyo Gosei Co., Ltd.

<Evaluation of positive photosensitive resin composition>
The positive photosensitive resin compositions (1) to (5) obtained above were each applied on a silicon wafer having a diameter of 5 inches with a spin coater, dried on a hot plate at 110 ° C. for 60 seconds, and had a thickness of about 1 μm. A thin film was formed. The obtained wafer with a coating film was immersed in various weak alkaline developers for 60 seconds, and then dried on a hot plate at 110 ° C. for 60 seconds. The film thickness before and after immersion in the developing solution was measured, and the value obtained by dividing the difference by 60 was evaluated as ADR (Å / s). The evaluation results are shown in Table 4. It can be said that the lower the value, the better the alkali solubility resistance of the unexposed portion.
-ADR6 (Å / s): Value when a developer (pH 12) consisting of 1 mass% sodium carbonate aqueous solution is used as a weak alkaline developer.-ADR7 (Å / s): 1 mass% as a weak alkaline developer. Value when a developer (pH 11), which is a mixture of an aqueous sodium carbonate solution and a 1 mass% sodium hydrogen carbonate solution at a mass ratio of 75/25, is used.-ADR8 (Å / s): 1 mass% carbonate as a weak alkaline developer. Value when a developer (pH 10), which is a mixture of an aqueous sodium solution and a 1 mass% sodium hydrogen carbonate solution at a mass ratio of 50/50, is used.-ADR9 (Å / s): 1 mass% sodium carbonate as a weak alkaline developer Value when a developer (pH 9), which is a mixture of an aqueous solution and a 1 mass% sodium hydrogen carbonate solution at a mass ratio of 25/75, is used.-ADR10 (Å / s): 1 mass% sodium hydrogen carbonate as a weak alkaline developer. Value when using a developer (pH 8) consisting of an aqueous solution

In addition, as reference values that contribute to the evaluation of fine pattern formability, the ADR values (ADR1 to 5) of the coating film made of each novolak-type phenol resin and the positive values measured in "Evaluation of alkali solubility of novolak-type phenol resin". The ratio (ADR1 / ADR6, ADR2 / ADR7, ADR3 / ADR8, ADR4 / ADR9, ADR5 / ADR10) to the ADR value of the coating film using the type photosensitive resin composition was evaluated as a contrast. The evaluation results are shown in Table 4. It can be said that the higher the contrast, the better the fine pattern forming property of the positive photosensitive resin composition.

As is clear from the results shown in Tables 1 and 2, the coating film made of the novolak type phenol resin (A-1) or (A-2) is excellent in heat resistance and alkali solubility. On the other hand, the coating film made of novolak type phenol resin (A') is inferior in heat resistance and alkali solubility.

As is clear from the results shown in Table 4, the coating film composed of the positive photosensitive resin compositions (1) to (4) using the novolak type phenol resin (A-1) or (A-2) is The unexposed portion has excellent alkali solubility resistance, and the novolak type phenolic resins (A-1) and (A-2) have excellent alkali solubility, so that the contrast is also high. On the other hand, the coating film made of the positive photosensitive resin composition (5) using the novolak type phenol resin (A') has a relatively low alkali solubility resistance in the unexposed portion, and the novolak type phenol resin (A). Since the alkali solubility of') is also low, the contrast is also low.

Claims (10)

1. A coating film forming process for forming a coating film on a substrate,
   A method for producing a resist pattern, comprising an exposure step of exposing the coating film and a developing step of developing the coating film with a dilute and weak alkaline developer after the exposure step.
   The coating film is derived from the phenolic hydroxyl group-containing compound using the phenolic hydroxyl group-containing compound containing the aromatic compound (a) represented by the following general formula (1) and the aldehyde compound as essential reaction raw materials. A method for producing a resist pattern, which comprises a novolak-type phenol resin (A) in which 80 mol% or more of the constituent units are the constituent units (a) derived from the aromatic compound (a), and a photosensitizer (B).
   

   

   
   [In the general formula (1), R ¹ and R ² independently represent an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group or a halogen atom. m, n and p each independently represent an integer of 0 to 4. When there are a plurality of R ¹ , the plurality of R ^1s may be the same or different from each other. When there are a plurality of R ^2s , the plurality of R ^2s may be the same or different from each other. R ³ represents a structural moiety having one or more substituents selected from an alkoxy group, a halogen group and a hydroxyl group on a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a hydrocarbon group. ^R4 represents a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group or a halogen atom. When there are a plurality of ^R4s , the plurality of ^R4s may be the same or different from each other. ]
2. The method for producing a resist pattern according to claim 1, wherein the pH of the dilute and weak alkaline developer in the developing step is in the range of 8.0 or more to 12.0 or less.
3. According to claim 1 or 2, the dilute and weak alkaline developer is a 0.1 to 10% by mass aqueous solution of an inorganic salt of an acid having a pKa in the range of 6.0 to 12.0 in _H2O at 23 ° C. The method for manufacturing the resist pattern described.
4. The production of the resist pattern according to any one of claims 1 to 3, wherein R ¹ and R ² of the novolak type phenol resin (A) are methyl groups, m and n are 2, and p is 0. Method.
5. The invention according to any one of claims 1 to 4, wherein 80 mol% or more of the structural unit derived from the aldehyde compound of the novolak-type phenol resin (A) is the structural unit (b) derived from an aliphatic aldehyde. A method for manufacturing a resist pattern.
6. The method for producing a resist pattern according to any one of claims 1 to 5, wherein the reaction solvent for producing the novolak type phenol resin (A) is a carboxylic acid compound.
7. The method for producing a resist pattern according to any one of claims 1 to 6, wherein the substrate is a transparent conductive film.
8. The method for producing a resist pattern according to claim 7, wherein the transparent conductive film contains zinc oxide.
9. A resist pattern manufactured by the method for manufacturing a resist pattern according to any one of claims 1 to 8.
10. An essential reaction raw material is a phenolic hydroxyl group-containing compound containing the aromatic compound (a) represented by the following general formula (1) and an aldehyde compound, and 80 mol of a constituent unit derived from the phenolic hydroxyl group-containing compound is used. Positive type photosensitive for manufacturing a transparent laminated member containing a novolak type phenol resin (A), a photosensitizer (B), and a solvent (C) in which% or more is a structural unit (a) derived from the aromatic compound (a). Phenol formaldehyde composition.
    

    

    
    [In the general formula (1), R ¹ and R ² independently represent an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group or a halogen atom. m, n and p each independently represent an integer of 0 to 4. When there are a plurality of R ¹ , the plurality of R ^1s may be the same or different from each other. When there are a plurality of R ^2s , the plurality of R ^2s may be the same or different from each other. R ³ represents a structural moiety having one or more substituents selected from an alkoxy group, a halogen group and a hydroxyl group on a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a hydrocarbon group. ^R4 represents a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group or a halogen atom. When there are a plurality of ^R4s , the plurality of ^R4s may be the same or different from each other. ]

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