TW202330684A - Phenolic hydroxyl group-containing resin including a structural unit (a) derived from a phenolic compound, a structural unit (b) derived from an aromatic aldehyde compound having a carboxyl group, and a structural unit (c) derived from an aromatic aldehyde compound - Google Patents

Abstract

To provide a photosensitive resin composition which has excellent solubility in an alkalescent developer, has high affinity to a photosensitive agent, and does not use formaldehyde. A phenolic hydroxyl group-containing resin includes: a structural unit (a) derived from a phenolic compound, a structural unit (b) derived from an aromatic aldehyde compound having a carboxyl group, and a structural unit (c) derived from an aromatic aldehyde compound, wherein the molar ratio of the structural unit (a), the structural unit (b) and the structural unit (c) is 0.5-1.5: 0.05-1.0: 0.1-1.5.

Description

Resins containing phenolic hydroxyl groups

The present invention relates to resins containing phenolic hydroxyl groups, photosensitive resin compositions, curable compositions and photoresist films using them.

As a photoresist used in the manufacture of semiconductors such as ICs and LSIs, the manufacture of display devices such as LCDs, and the manufacture of original printing plates, photoresists using alkali-soluble resins and 1,2-diazonaphthoquinone compounds are known. Positive type photosensitive resin composition. In the field of photoresist, various photoresist pattern formation methods that are subdivided according to the application and function have been successively developed. Along with this, the required performance of the photoresist resin material is also complicated and diversified.

Tetramethylammonium hydroxide is widely used as a developer of a positive photosensitive resin composition, but it has high toxicity and a large environmental load. In recent years, in order to reduce the environmental load, positive-type photosensitive resin compositions that can be developed with weakly alkaline developing solutions such as sodium carbonate and sodium bicarbonate that have low environmental load, and that do not use environmental load substances such as formaldehyde, are being sought. In addition, semiconductors have become more highly integrated, and there is a tendency for pattern refinement, and better sensitivity is being sought.

Regarding the above-mentioned problems, for example, Patent Document 1 discloses a positive-type photosensitive resin composition capable of being developed with a weakly alkaline developer, which is a combination of a carboxylic acid-containing phenol resin and a diazonaphthoquinone photosensitive agent.

On the other hand, as a method of forming an electrode pattern composed of a transparent conductive film on a transparent substrate, a method is known in which a photosensitive layer containing a positive photosensitive resin composition is formed on a substrate. On the transparent conductive film, expose the photosensitive layer through a mask, remove the exposed part of the photosensitive layer by developing the photosensitive layer, and etch the exposed transparent conductive film to remove the remaining photosensitive layer.

In recent years, due to the depletion of In, it is being studied to replace ITO used as a transparent conductive film of an electrode, to use ZnO or to add a metal to ZnO (hereinafter referred to as "ZnO-based thin film"). Since ZnO-based thin films are damaged by strong alkalis, it is known that conventional strong alkaline developing solutions cannot produce practical electrode patterns. Therefore, research and development of a positive-type photosensitive resin composition that does not damage the ZnO-based film and can make fine electrode patterns with weakly alkaline developing solutions such as sodium carbonate and sodium bicarbonate (for example, Patent Document 2). [Prior Art Literature] [Patent Document]

Patent Document 1 Japanese Unexamined Patent Application Publication No. 2001-114853 Patent Document 2 Japanese Patent Laid-Open No. 2008-112134

[Problem to be solved by the invention]

The positive-type photosensitive resin composition described in Patent Document 1 cannot obtain a sufficient dissolution rate in a weak alkaline developer, and also cannot obtain sensitivity corresponding to miniaturization. Moreover, since various heat treatments are applied in the manufacturing steps of semiconductors and the like, high heat resistance is also sought, but the positive-type photosensitive resin composition described in Patent Document 1 has a problem of not having sufficient heat resistance. The positive-type photosensitive resin composition described in Patent Document 2 cannot obtain a sufficient dissolution rate in a weakly alkaline developer, and lacks affinity with a photosensitive agent, making it unsuitable for drawing fine patterns. The positive-type photosensitive resin compositions described in Patent Documents 1 and 2 have a problem that formaldehyde, which is an environmental load substance, is used.

As mentioned above, from the viewpoint of reducing the environmental load and the formation of fine electrode patterns on ZnO-based thin films, etc., the development of a positive-type photosensitive resin composition that exhibits excellent solubility in a weakly alkaline developer is being sought. , and has high affinity with photosensitizer, high heat resistance, and does not use environmental load substances such as formaldehyde.

The purpose of the present invention is to provide a photosensitive resin composition, which has excellent solubility to weak alkaline developer, has high affinity with photosensitizer, and does not use formaldehyde. Also, an object of the present invention is to provide a curable material capable of obtaining a photoresist film having high heat resistance. [Means to solve the problem]

As a result of diligent research by the present inventors to solve the above-mentioned problems, it was found that a structural unit (a) derived from a phenolic compound, a structural unit (b) derived from an aromatic aldehyde compound having a carboxyl group, and a structural unit derived from an aromatic compound were used. The composition of the phenolic hydroxyl group-containing resin of the structural unit (c) of the aldehyde compound has excellent solubility in a weak alkaline developing solution and high affinity with a photosensitive agent, and the present invention has been completed. Formaldehyde was not used in the synthesis of the phenolic hydroxyl-containing resin.

That is, the present invention relates to a phenolic hydroxyl-containing resin comprising a structural unit (a) derived from a phenolic compound, a structural unit (b) derived from an aromatic aldehyde compound having a carboxyl group, and a structural unit (b) derived from an aromatic aldehyde compound. Structural unit (c) of an aldehyde compound. Moreover, the present invention also relates to a photosensitive resin composition comprising the aforementioned resin containing phenolic hydroxyl groups and a diazoquinone-based photosensitive agent. Moreover, the present invention also relates to a photoresist film obtained from the aforementioned photosensitive resin composition. Moreover, the present invention also relates to a curable composition comprising the aforementioned phenolic hydroxyl group-containing resin and a curing agent. Moreover, the present invention also relates to a cured product of the aforementioned curable composition. Moreover, the present invention also relates to a method for manufacturing a photoresist pattern, which includes: a coating film forming step of forming a coating film composed of the aforementioned photosensitive resin composition on a substrate; an exposing step of exposing the aforementioned coating film; And a developing step of developing the aforementioned coating film after the aforementioned exposure step with a dilute weak alkaline developing solution. [Effect of Invention]

According to the present invention, it is possible to provide a photosensitive resin composition which has excellent solubility in a weak alkaline developer, has high affinity with a photosensitive agent, and does not use formaldehyde. In addition, a curable material capable of obtaining a photoresist film having high heat resistance can be provided.

[Mode for Carrying Out the Invention]

Embodiments for implementing the present invention will be described below. However, in this specification, "x~y" means the numerical range of "more than x and less than y". The upper limit and lower limit described about the numerical range can be combined arbitrarily. Moreover, the aspect which combined two or more of the various aspects of this invention described below is also the aspect of this invention.

[Resins containing phenolic hydroxyl groups] A phenolic hydroxyl group-containing resin according to one embodiment of the present invention includes the following structural units (a) to (c). Structural unit (a): a structural unit derived from a phenolic compound Structural unit (b): A structural unit derived from an aromatic aldehyde compound having a carboxyl group Structural unit (c): A structural unit derived from an aromatic aldehyde compound (without carboxyl group)

The said structural unit (a) contributes to the affinity with a photosensitizer and heat resistance. The above-mentioned structural unit (b) contributes to the solubility and heat resistance to the weak alkaline developing solution. The structural unit (c) contributes to affinity with a photosensitizer and heat resistance.

In this embodiment, the presence ratio (molar ratio, structural unit (a):structural unit (b):structural unit (c)) of structural unit (a), structural unit (b) and structural unit (c) is better 0.5 to 1.5: 0.05 to 1.0: 0.1 to 1.5. More preferably, it is 1.0:0.05 to 1.0:0.1 to 1.5, and particularly preferably, it is 1.0:0.1 to 0.6:0.3 to 1.2. The existence ratio can be adjusted by the addition ratio of the raw material compounds.

As for the structural unit (a), the phenol compound is preferably a compound represented by the following formula (1). (In formula (1), R ₁ is an aliphatic hydrocarbon group, an alkoxy group, an aryl group, an aralkyl group or a halogen atom. l is an integer of 0 to 2, and m is 1 or 2.)

The aliphatic hydrocarbon group of R ₁ in the above formula (1) includes an alkyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. The number of carbon atoms is preferably, for example, 1-9. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and cyclohexyloxy. The number of carbon atoms is preferably, for example, 1-9.

Examples of the aryl group include those having 6 to 14 carbon atoms forming a ring. The aryl group may have substituents such as the above-mentioned alkyl group, alkoxy group, and hydroxyl group. Specifically, phenyl, hydroxyphenyl, dihydroxyphenyl, hydroxyalkoxyphenyl, alkoxyphenyl, tolyl, xylyl, naphthyl, hydroxynaphthyl, dihydroxynaphthyl .

The aralkyl group means an alkyl group in which one or more hydrogen atoms of the alkyl group (C _n H _2n+1 ) are substituted with an aryl group. The aryl group may have substituents such as the above-mentioned alkyl group, alkoxy group, and hydroxyl group. Specifically, benzyl, hydroxybenzyl, dihydroxybenzyl, tolylmethyl, xylylmethyl, naphthylmethyl, hydroxynaphthylmethyl, dihydroxynaphthylmethyl, benzene Ethyl, hydroxyphenylethyl, dihydroxyphenethyl, cresylethyl, xylylethyl, naphthylethyl, hydroxynaphthylethyl, dihydroxynaphthylethyl. The number of carbon atoms is preferably, for example, 7-15. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

In one embodiment, R ₁ is an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Methyl is preferred. Also, l is preferably 1.

Specific examples include o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, p-octylphenol, p-tertiary butylphenol, o-cyclohexylphenol, m-cyclo Monoalkylphenols such as hexylphenol and p-cyclohexylphenol; 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,4-xylenol, 2,6-di Dialkylphenols such as cresol, etc. Among these, monoalkylphenol is preferable, and o-cresol, m-cresol, and p-cresol are more preferable.

The same structure may be used individually for a phenol compound, and the compound of several types which have a different molecular structure may be used.

As for the structural unit (b), the aromatic aldehyde compound having a carboxyl group is preferably a compound represented by the following formula (2). (In formula (2), R ₂ is a group selected from the group comprising aliphatic hydrocarbon group, alkoxy group, halogen atom, cyano group, and nitro group, and q is an integer of 0 to 4.)

Examples of the aliphatic hydrocarbon group of R2 in the above formula ( ₂ ) include alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and cyclohexyl. The number of carbon atoms is preferably, for example, 1-9. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and cyclohexyloxy. The number of carbon atoms is preferably, for example, 1-9.

q is an integer of 0-4, preferably 0 or 1.

Specific examples include: 4-formylbenzoic acid, 2-formylbenzoic acid, 3-formylbenzoic acid, methyl 4-formylbenzoate, ethyl 4-formylbenzoate Esters, Propyl 4-formylbenzoate, Isopropyl 4-formylbenzoate, Butyl 4-formylbenzoate, Isobutyl 4-formylbenzoate, 4-Formylphenyl Tertiary butyl formate, cyclohexyl 4-formylbenzoate, tertiary octyl 4-formylbenzoate, etc. Among these, 4-formylbenzoic acid is preferred. The aromatic aldehyde which has a carboxyl group may be used individually by 1 type, and may use 2 or more types together.

Regarding the structural unit (c), the aromatic aldehyde compound in this embodiment is preferably a compound represented by the following formula (3). (In formula (3), R ₃ is a group selected from the group including aliphatic hydrocarbon group, alkoxy group, halogen atom, cyano group, and nitro group, n is an integer of 0 to 3, and p is 0 to 3 integer of 2.)

Examples of the aliphatic hydrocarbon group of R3 in the above formula ( ₃ ) include alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and cyclohexyl. The number of carbon atoms is, for example, preferably 1-9, more preferably 1-5. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and cyclohexyloxy. The number of carbon atoms is, for example, preferably 1-9, more preferably 1-5.

n is an integer of 0-3, preferably 0 or 1. p is an integer of 0-2, preferably 0 or 1.

Examples of the aromatic aldehyde include willoxal, benzaldehyde, 2-chlorobenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-methoxybenzaldehyde, and 3-nitrobenzaldehyde. The aromatic aldehyde is preferably willoxal or benzaldehyde. Aromatic aldehydes may be used alone or in combination of two or more. In one embodiment, the aromatic aldehyde preferably has a hydroxyl group at the ortho-position of the carbonyl group.

In the phenolic hydroxyl group-containing resin of this embodiment, the total content of the above-mentioned structural units (a), (b) and (c) has excellent solubility in a weak alkaline developing solution and high affinity with a photosensitive agent. In terms of properties, it is preferably at least 30% by mass, more preferably at least 50% by mass, and still more preferably at least 90% by mass. The total content of the structural units (a), (b) and (c) may be substantially 100% by mass. Here, substantially 100% by mass means that structural units other than the above-mentioned structural units (a), (b) and (c) are unavoidably included.

The weight average molecular weight of the phenolic hydroxyl-containing resin of this embodiment is preferably 1,000 or more, more preferably 1,500 or more. Moreover, it is preferably 10,000 or less, more preferably 9,000 or less, still more preferably 8,000 or less. When a weight average molecular weight is 1000 or more, since heat resistance is high, it is preferable. On the other hand, when the weight average molecular weight is 8,000 or less, it is preferable because sensitivity is high. However, in this specification, the weight average molecular weight is measured according to the conditions described in an Example.

The phenolic hydroxyl-containing resin of this embodiment is obtained by polycondensing the above-mentioned phenolic compound, an aromatic aldehyde compound having a carboxyl group, and an aromatic aldehyde compound in a solvent with an acid catalyst.

The mol ratio (phenolic compound: aromatic aldehyde compound with carboxyl group: aromatic aldehyde compound) of the phenolic compound in the solvent, the aromatic aldehyde compound with carboxyl group, and aromatic aldehyde compound, obtains to weak alkaline developing solution from From the viewpoint of excellent solubility and heat-resistant cured film, it is preferably in the range of 1.0:0.05-1.0:0.1-1.5, more preferably in the range of 1.0:0.1-0.6:0.3-1.2.

With respect to the total mass of the starting materials of the resin containing phenolic hydroxyl groups, the ratio of the total mass of the phenolic compound, the aromatic aldehyde compound having a carboxyl group, and the total mass of the aromatic aldehyde compound in the solvent is obtained from the weak alkaline developer. From the viewpoint of obtaining a cured film having heat resistance in addition to the solubility, it is preferably at least 30% by mass, more preferably at least 50% by mass, and still more preferably substantially 100% by mass.

Examples of the acid catalyst include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts may be used alone or in combination of two or more. From the viewpoint of excellent activity, sulfuric acid and p-toluenesulfonic acid are preferable. However, the acid catalyst may be added before the reaction, or may be added during the reaction.

As the solvent used in the manufacture of resins containing phenolic hydroxyl groups, for example: carboxylic acid compounds such as formic acid, acetic acid, propionic acid, butyric acid, and valerian acid; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl Glycol ether compounds such as glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monophenyl ether; 1,3-diol Cyclic ether compounds such as dioxane and 1,4-dioxane; 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 wait. These solvents may be used alone or in combination of two or more. From the viewpoint of excellent solubility of the obtained compound, acetic acid is preferred.

The amount of the solvent used is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, based on 100 parts by mass of the raw material of the phenolic hydroxyl group-containing resin from the viewpoint of reaction uniformity. Moreover, it is preferably at most 500 parts by mass, more preferably at most 300 parts by mass.

The reaction temperature at the time of polycondensing the raw material of the phenolic hydroxyl group-containing resin is preferably 30°C or higher, more preferably 40°C or higher, in order to efficiently increase the molecular weight while accelerating the reaction. In addition, it is preferably at most 100°C, more preferably at most 80°C. The reaction time is preferably at least 4 hours, more preferably at least 12 hours. Moreover, it is preferably 32 hours or less, more preferably 24 hours or less.

After the reaction is finished, the product is recovered by, for example, reprecipitation operation, whereby a resin containing phenolic hydroxyl groups can be obtained. Examples of poor solvents used in reprecipitation include: water; monohydric alcohols such as methanol, ethanol, and propanol; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, and cyclohexane; toluene, xylene and other aromatic hydrocarbons. Among these poor solvents, water and methanol are preferable from the viewpoint of efficiently removing the acid catalyst at the same time.

In order to increase the purity of the phenolic hydroxyl group-containing resin, the reprecipitation operation may be performed two or more times. In this case, examples of solvents for dissolving the resin containing phenolic hydroxyl groups include: monohydric alcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4- Butanediol, 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 monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethyl alcohol Glycol ethers such as glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monophenyl ether; cyclic ethers such as 1,3-dioxane and 1,4-dioxane; Glycol esters such as ethylene glycol acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. In the case of using water as the poor solvent, the redissolving solvent is preferably acetone. Among them, the poor solvent and the solvent may be used alone or in combination of two or more.

The phenolic hydroxyl-containing resin of the present invention can be used in various electrical and electronic components such as adhesives, coatings, photoresists, and printed circuit boards.

[Photosensitive resin composition] A photosensitive resin composition according to an embodiment of the present invention includes the phenolic hydroxyl-containing resin (hereinafter also referred to as phenolic hydroxyl-containing resin (A)) of the present invention, and a diazide-quinone-based photosensitive agent (hereinafter also referred to as Sensitizer (B)). Since the resin (A) containing a phenolic hydroxyl group has high affinity with a diazide quinone photosensitive agent, it becomes a highly sensitive photosensitive resin composition.

The blending amount of the phenolic hydroxyl-containing resin (A) in the photosensitive resin composition of this embodiment is preferably in the range of 50 to 99% by mass relative to the total resin solid content of the photosensitive resin composition. It is preferably in the range of 60 to 95% by mass, more preferably in the range of 70 to 90% by mass.

The diazoquinone-based photosensitizer of the photosensitive agent (B) contains a compound having a diazoquinone group. Specific examples of compounds having a diazoquinone group include, for example, aromatic (poly)hydroxyl compounds and 1,2-diazonaphthoquinone-5-sulfonic acid, 1,2-diazonaphthoquinone-4- Complete esterification, partial esterification, amidation or partial amidation of sulfonic acid, o-diazoanthraquinone sulfonic acid, etc.

Examples of aromatic (poly)hydroxy compounds include: 2,3,4-trihydroxydiphenyl ketone, 2,4,4'-trihydroxydiphenyl ketone, 2,4,6-trihydroxydiphenyl Ketone, 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'-pentahydroxy Benzophenone, 2,2',3,4,5-pentahydroxybenzophenone, 2,3',4,4',5',6-hexahydroxybenzophenone, 2,3,3 Polyhydroxybenzophenone compounds such as ',4,4',5'-hexahydroxybenzophenone;

Bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(2', 3',4'-trihydroxyphenyl)propane, 4,4'-{1-[4-[2-(4-hydroxyphenyl)-2-propyl]phenyl]ethylene}bisphenol, 3,3'-Dimethyl-{1-[4-[2-(3-methyl-4-hydroxyphenyl)-2-propyl]phenyl]ethylene}bisphenol Poly)hydroxyphenyl]alkane compounds;

Reference (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-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)- 3,4-Dihydroxyphenylmethane and other ginseng (hydroxyphenyl)methane compounds or their methyl substitutes;

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-hydroxyl- 2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2- hydroxyphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3 -Methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxy Phenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-2-hydroxy-4-methylphenyl) Bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methane compounds such as -2-hydroxyphenylmethane, bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane, etc. or its methyl substituted, etc. These photosensitizers may be used individually, respectively, and may use 2 or more types together.

The blending amount of the photosensitive agent (B) in the photosensitive resin composition of the present embodiment is relatively small relative to the total resin solid content of the photosensitive resin composition in order to obtain a photosensitive resin composition with excellent photosensitivity. It is preferably at least 5% by mass, more preferably at least 10% by mass. Also, it is preferably at most 50% by mass, more preferably at most 30% by mass.

The photosensitive resin composition of the present embodiment preferably further includes: a calix structure having a structural unit (a) derived from a phenolic compound and a structural unit (b) derived from an aromatic aldehyde compound having a carboxyl group Phenolic resin (hereinafter also referred to as phenolic hydroxyl group-containing resin (C)).

The phenolic hydroxyl group-containing resin (C) is a phenolic hydroxyl group-containing resin represented by the following general formula (C).

(In the aforementioned general formula (C), R ²¹ is an alkyl group, an alkoxy group or an aryl group, R ²² is an aryl group having a carboxyl group, p is an integer of 1 to 3, and q is an integer of 2 to 15. When p is In the case of 2 or more, a plurality of R ²¹ may be the same as or different from each other.)

The phenolic hydroxyl group-containing resin (C) can be obtained by polycondensing the phenolic compound described in the phenolic hydroxyl group-containing resin (A) and an aromatic aldehyde compound having a carboxyl group using an acid catalyst in a solvent.

The weight average molecular weight of the phenolic hydroxyl group-containing resin (C) is preferably at least 1,000, more preferably at least 1,500. Moreover, it is preferably at most 25,000, more preferably at most 20,000, and still more preferably at most 10,000.

The blending amount of the phenolic hydroxyl group-containing resin (C) in the photosensitive resin composition of this embodiment is, for example, preferably in the range of 5 to 20% by mass relative to the total resin solid content of the photosensitive resin composition. It is in the range of 5-15 mass %, more preferably in the range of 7-15 mass %, still more preferably in the range of 10-13 mass %.

When the photosensitive resin composition of this embodiment is used for photoresists, in addition to the phenolic hydroxyl group-containing resin (A), photosensitizer (B) and optional phenolic hydroxyl group-containing resin (C), If necessary, various additives such as other compounds containing phenolic hydroxyl groups, pigments, dyes, leveling agents, filling materials, crosslinking agents, dissolution accelerators, curing agents, curing accelerators, etc. can be added, and dissolved in The photoresist resin composition is made in an organic solvent. The photoresist resin composition can be used as a positive photoresist solution as it is, and can also be used as a positive photoresist film obtained by coating the photoresist resin composition into a thin film and removing the solvent. The support film when used as a photoresist film includes synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. The support film can be a single-layer film or a laminated film. In addition, the surface of the support film may be corona-treated or coated with a release agent.

Examples of organic solvents include: N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl Polar aprotic solvents such as argon, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether and other ethers, acetone, methyl ethyl ketone, diisobutyl ketone and other ketones, ethyl acetate, butyl acetate, acetic acid Isobutyl ester, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate and other esters, ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl- Alcohols such as 3-methoxybutanol, aromatic hydrocarbons such as toluene and xylene, etc. These organic solvents may be used alone or in combination of two or more.

The content of the organic solvent in the photosensitive resin composition is preferably adjusted so that the solid content concentration in the composition is 5% by mass or more and 65% by mass or less. Thereby, the fluidity|fluidity of a photosensitive resin composition becomes sufficient, and a uniform coating film can be obtained by coating methods, such as a spin coating method.

Other phenolic hydroxyl group-containing compounds may be compounds other than the phenolic hydroxyl group-containing resin (A) and the phenolic hydroxyl group-containing resin (C). Examples of other phenolic hydroxyl-containing compounds include compounds containing phenolic hydroxyl groups such as phenol, cresol, naphthol, biphenol, bisphenol, and triphenylmethane, phenol novolac resins, and cresol novolac resins. , bisphenol novolac and other phenolic resins. These may be used individually, respectively, and may use plural types together.

The ratio of the phenolic hydroxyl-containing resin (A) to the total of the phenolic hydroxyl-containing resin (A), the phenolic hydroxyl-containing resin (C), and other phenolic hydroxyl-containing compounds is preferably 50% by mass Above, more preferably at least 80% by mass, especially preferably at least 90% by mass.

The photosensitive resin composition of this embodiment can be made uniform by stirring and mixing the resin (A) containing phenolic hydroxyl group, photosensitizer (B), and organic solvent, and various additives added as necessary. liquid to prepare.

When blending solid substances such as fillers and pigments into the photosensitive resin composition, it is preferable to disperse and mix them using a dispersing device such as a dissolver, a homogenizer, and a three-roll mill. In addition, in order to remove coarse particles and impurities, the composition may be filtered using a mesh filter, a filter membrane, or the like.

[curable composition] A curable composition according to one embodiment of the present invention includes the above-mentioned phenolic hydroxyl group-containing resin (A) of the present invention, and a curing agent. The curing agent used in this embodiment is not particularly limited as long as it is a compound capable of causing a curing reaction with the phenolic hydroxyl group-containing resin of the present invention, and various compounds can be used. Also, the curing method of the curable composition is not particularly limited, and it can be cured by an appropriate method such as thermal curing or photocuring according to the type of curing agent, the type of curing accelerator, and the like. Curing conditions such as the heating temperature and time during thermal curing, the type of light during photocuring, and the exposure time are appropriately adjusted according to the type of curing agent, the type of curing accelerator described later, and the like.

Examples of the curing agent used in this embodiment include urea resin, melamine resin, furan resin, xylene resin, epoxy resin, unsaturated polyester resin, thermosetting polyimide, thermosetting Polyamideimide, etc. In one embodiment, a curing agent and a curing accelerator may also be formulated together. As the curing accelerator, a conventional one known to accelerate the curing reaction can be used according to the curing agent used. In the case of using these curing agents and curing accelerators, after forming a photoresist pattern by the method described later, heating or the like will result in a more highly heat-resistant photoresist film.

The compounding amount of the curing agent in the curable composition of the present embodiment is based on 100 parts by mass of the total of the phenolic hydroxyl group-containing resin of the present invention and other resins (X) described later in order to obtain a composition having excellent curability , the ratio is preferably 0.5 to 50 parts by mass.

In the curable composition of this embodiment, in addition to the resin (A) containing a phenolic hydroxyl group and the curing agent, the photosensitizer (B) and others described above for the photosensitive resin composition of the present invention can be used if necessary. Compounds containing phenolic hydroxyl groups, pigments, dyes, leveling agents and other surfactants, fillers, cross-linking agents, dissolution accelerators and other additives, organic solvents. Examples of various additives and organic solvents are the same as those of the above-mentioned photosensitive resin composition.

In one embodiment, the curable composition may be used in combination with other resin (X) in addition to the above-mentioned phenolic hydroxyl group-containing resin of the present invention. Examples of the resin (X) include various novolac resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenolic compounds, compounds containing phenolic hydroxyl groups, and aromatic compounds containing alkoxy groups. Modified novolak resin, phenol arane resin (XYLOK resin), naphthol arane resin, trimethylol methane resin, tetraphenol ethane resin, biphenyl modified phenol resin, biphenyl modified naphthalene Phenolic resin, amino three Modified phenolic resins, various vinyl polymers.

In the case of using other resin (X), the compounding ratio of the phenolic hydroxyl group-containing resin of the present invention and the resin (X) can be set arbitrarily according to the application. For example, the ratio of the resin (X) is preferably 0.5 to 100 parts by mass relative to 100 parts by mass of the phenolic hydroxyl group-containing resin of the present invention.

The curable composition of this embodiment can be prepared by stirring and mixing the phenolic hydroxyl group-containing resin (A), a curing agent, an organic solvent, and various additives as needed to form a homogeneous liquid.

To form a cured film from the curable composition of this embodiment, for example, there is the following method: apply the curable composition on an object to be subjected to photolithography such as a silicon substrate, and dry it at a temperature of 100 to 200°C. Further, it is heated and cured at a temperature of 250 to 400°C. A photoresist pattern produced by a multilayer photoresist method can be formed by performing a general photolithography operation on the cured film to form a photoresist pattern, and then performing dry etching treatment with a halogen-based plasma gas or the like.

[Manufacturing method of photoresist pattern] A method for producing a photoresist pattern according to an embodiment of the present invention includes a coating film forming step of forming a coating film composed of the photosensitive resin composition of the present invention on a substrate, an exposing step of exposing the coating film to light, and The development step of developing the coating film after the exposure step with a dilute weak alkaline developer.

(1) Coating film formation step The coating film forming step is a step of forming a coating film on a substrate. Examples of the base material include silicon substrates, silicon carbide substrates, gallium nitride substrates, and the like. In this embodiment, since the dilute weak alkaline developer is used, even if the substrate has a transparent conductive film made of ZnO thin film, a fine photoresist pattern with high heat resistance can be obtained. The coating film can be formed by coating a photosensitive resin composition (photoresist resin composition) on an object such as a substrate subjected to photolithography, and prebaking at a temperature of 60-150°C. Examples of the coating method include spin coating, roll coating, flow coating, dip coating, spray coating, doctor blade coating, and the like.

(2) Exposure steps The exposure step is a step of exposing the coating film through a mask on which a pattern is drawn. As a light source which exposes a coating film, infrared light, visible light, ultraviolet light, deep ultraviolet light, X-ray, an electron beam, etc. are mentioned, for example. Among these light sources, ultraviolet light is preferred, and g-line (wavelength 436nm) and i-line (wavelength 365nm) of high-pressure mercury lamps are suitable.

(3) Development step The development step is a step of developing the coating film after the exposure step with a dilute weak alkaline developer. In the developing step, a photoresist pattern is formed by developing the coating film after the exposure step with a dilute weak alkaline developing solution. Since the phenolic hydroxyl group-containing resin (A) contained in the coating film has excellent alkali solubility, it can be developed sufficiently even when using a dilute weak alkaline developing solution. At the same time, since the resin (A) containing phenolic hydroxyl group has excellent compatibility with the photosensitive agent (B), the alkali solubility in the unexposed part is very high. The contrast is high, and fine patterns can be drawn. In addition, by using a dilute weak alkaline developing solution in the developing step, the photoresist pattern can be developed while suppressing damage to the ZnO-based thin film.

In this specification, the dilute weak alkaline developing solution means the 0.1-10 mass % aqueous solution of the inorganic salt of the acid whose pKa in 23 degreeC _H2O in the range of 6.0-12.0. Sodium carbonate, sodium bicarbonate, etc. are mentioned as an inorganic acid. The pH of the dilute weak alkaline developer used in the developing step is preferably not less than 8.0 and not more than 12.0.

In the case of using a mixture of sodium carbonate aqueous solution and sodium bicarbonate aqueous solution as a dilute weak alkaline developer, the mixing ratio of the two is not particularly limited, and can be used in any ratio. Wherein, from the perspective of obtaining a particularly high contrast, the mass ratio of the two [(sodium carbonate aqueous solution)/(sodium bicarbonate aqueous solution)] is preferably in the range of 80/20～20/80, more preferably at 80/ 20 ~ 60/40 range. [Example]

Hereinafter, specific examples are given to further describe the present invention in detail. Here, the number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity (Mw/Mn) of the synthesized resin were measured under the following GPC measurement conditions. [Measurement conditions of GPC] Measuring device: "HLC-8220 GPC" manufactured by TOSOH Co., Ltd. String: "Shodex KF802" manufactured by Showa Denko Co., Ltd. (8.0mmФ×300mm) + "Shodex KF802" manufactured by Showa Denko Co., Ltd. (8.0mmФ×300mm) + "Shodex KF803" manufactured by Showa Denko Co., Ltd. (8.0mmФ×300mm) + "Shodex KF804" manufactured by Showa Denko Co., Ltd. (8.0mmФ×300mm) Column temperature: 40°C Detector: RI (differential refractor) Data processing: "GPC-8020 Model II Version 4.30" manufactured by TOSOH Co., Ltd. Developing solvent: tetrahydrofuran Flow rate: 1.0mL/min Sample: A product obtained by filtering a tetrahydrofuran solution of 0.5% by mass in terms of resin solid content with a microfilter Injection volume: 0.1mL Standard sample: the following monodisperse polystyrene (Standard sample: monodisperse polystyrene) "A-500" manufactured by TOSOH Co., Ltd. "A-2500" manufactured by TOSOH Co., Ltd. "A-5000" manufactured by TOSOH Co., Ltd. Made by TOSOH Co., Ltd. "F-1" Made by TOSOH Co., Ltd. "F-2" "F-4" made by TOSOH Co., Ltd. "F-10" made by TOSOH Co., Ltd. "F-20" manufactured by TOSOH Co., Ltd.

In addition, the measurement conditions of ¹³ C-NMR are as follows. [Measuring conditions of ¹³ C-NMR] Device: JNM-ECA500 manufactured by JEOL Ltd. Measuring mode: inverse gated decoupling (inverse gated decoupling) Solvent: deuterated dimethyl sulfone Pulse angle: 30° pulse Sample concentration: 30 mass % Number of accumulations: 4000 times Standard of chemical shift: Peak of dimethyl sulfone: 39.5ppm

[Resin containing phenolic hydroxyl group] Example 1 In a 4-necked flask with a capacity of 250 ml provided with a condenser, 18.3 g of m-cresol, 6.4 g of formylbenzoic acid and 15.7 g of salicaldehyde were added to make it Dissolve in 60g of acetic acid. While cooling in an ice bath, 2 ml of sulfuric acid was added. After raising the temperature to 80° C. with an oil bath, it was heated for 4 hours, and stirred continuously to make it react. After the reaction, the obtained solution was reprecipitated with water to obtain a crude product. The crude product was redissolved in acetone, and after further reprecipitation operation with water, the resulting product was filtered and vacuum-dried to obtain 32.1 g of orange powder containing phenolic hydroxyl resin (novolac resin) (A-1 ). As a result of the GPC measurement, the number average molecular weight (Mn) of the resin (A-1) was 1905, the weight average molecular weight (Mw) was 3600, and the polydispersity (Mw/Mn) was 1.89. Also, it was confirmed by ¹³ C-NMR that it contained a carboxyl group (166 to 168 ppm). The GPC spectrum is shown in FIG. 1 , and ^{the 13} C-NMR spectrum is shown in FIG. 2 . The abundance ratio of the structural unit (a) derived from m-cresol, the structural unit (b) derived from formylbenzoic acid, and the structural unit (c) derived from salicaldehyde (a:b:c, molar ratio) is 1.00:0.25:0.76.

In addition to the novolak resin (A-1), it was confirmed that a resin (caliciform resin) (C-1) containing a phenolic hydroxyl group derived from m-cresol and formylbenzoic acid (C-1) was obtained (GPC spectrum in Fig. 1 the right peak). The yield of the obtained phenolic hydroxyl group-containing resin (C-1) was 4.9 g, and the weight average molecular weight was 942.

Example 2 Except having changed formyl benzoic acid into 12.9 g, and amylaldehyde into 10.5 g, it carried out similarly to Example 1, and obtained 31.2 g of phenolic hydroxyl group containing resin (A-2). Mn of resin (A-2) was 1724, Mw was 2692, and Mw/Mn was 1.56. Also, it was confirmed by ¹³ C-NMR that it contained a carboxyl group (166 to 168 ppm). The GPC spectrum is shown in FIG. 3 , and the ¹³ C-NMR spectrum is shown in FIG. 4 . The abundance ratio of the structural unit (a) derived from m-cresol, the structural unit (b) derived from formylbenzoic acid, and the structural unit (c) derived from salicaldehyde (a:b:c, molar ratio) is 1.00:0.51:0.51.

In addition to the novolak resin (A-2), it was confirmed that a resin (caliciform resin) (C-2) containing a phenolic hydroxyl group derived from m-cresol and formylbenzoic acid (C-2) was obtained (GPC spectrum in Fig. 3 the right peak). The yield of the obtained phenolic hydroxyl group-containing resin (C-2) was 4.1 g, and the weight average molecular weight was 942.

Comparative Synthesis Example 1 In the reactor equipped with stirrer, reflux condenser and thermometer, add 108g o-cresol, 100g glyoxylic acid aqueous solution (glyoxylic acid content 40%), 140g diethylene glycol dimethyl ether, 2.2g The p-toluenesulfonic acid was reacted at 100°C under stirring. Next, 108 g of o-cresol and 120 g of diethylene glycol dimethyl ether were added, while stirring at 90° C., 102.2 g of formalin aqueous solution (formaldehyde content rate: 37%) was added dropwise, under reflux for 6 hours, and then It heated up to 150 degreeC and made it react. 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 resin powder (A-3).

Comparative synthesis example 2 Except not having used formylbenzoic acid, except having changed salicyral into 20.9g, it carried out similarly to Example 1, and obtained 31.2g of novolac resin (A-4) powders. It was confirmed by ¹³ C-NMR that there was no carboxyl group (166 to 168 ppm). ^{The 13} C-NMR spectrum is shown in Fig. 5 .

[Photoresist composition] Embodiment 3,4 Comparative example 1,2 20 g of the resin powder containing phenolic hydroxyl group synthesized in the examples and comparative synthesis examples shown in Table 1 was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA) to obtain a photoresist resin composition.

The following items were evaluated for the resist resin compositions obtained in Examples and Comparative Examples. The results are shown in Table 1. (1) heat resistance The photoresist composition was coated on a silicon wafer with a diameter of 5 inches by a spin coater, and then dried at 110° C. for 60 seconds to obtain a film with a thickness of 1 μm. This film was scraped off, and the glass transition temperature (hereinafter abbreviated as "Tg") was measured. Tg was measured using a differential scanning calorimeter ("Differential Scanning Calorimeter (DSC) Q100" manufactured by TA Instruments Co., Ltd.) in a nitrogen atmosphere at a temperature range of -100 to 300°C and a heating rate of 10°C/min conditions. The evaluation criteria are as follows. ○: Tg is 150°C or higher ×: Tg is less than 150°C

(2) Alkali solubility The photoresist composition prepared in each example was coated on a 5-inch silicon wafer with a thickness of about 1 μm by a spin coater, and dried on a heating plate at 110° C. for 60 seconds. The wafer on which the thin film was formed was immersed in a developer solution (D-1) "1% sodium carbonate aqueous solution (pH 12)" or a developer solution (D-2) "1% sodium bicarbonate aqueous solution (pH 8)" for 60 seconds. After dipping, the wafer was dried on a hot plate at 100°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 (ADR: Å/s) was calculated and evaluated. ADR1 is the value of developer (D-1), and ADR2 is the value of developer (D-2). The evaluation criteria are as follows. ○: ADR is over 100 ×: ADR is less than 100

(3) Environmental load When synthesizing a resin containing a phenolic hydroxyl group, the case where formaldehyde was not used was rated as ○, and the case where formaldehyde was used during resin synthesis was rated as x.

[Table 1] use resin Glass transition temperature Tg(℃) Alkali solubility (Å/s) environmental load Developer D-1: ADR1 Developer D-2: ADR2 Example 3 Example 1 180: ○ 3810: ○ 150: ○ ○ Example 4 Example 2 190: ○ 4780: ○ 220: ○ ○ Comparative example 1 Comparative Synthesis Example 1 110: × 1620: ○ 30: × x Comparative example 2 Comparative Synthesis Example 2 140: × 480: ○ 10: × ○

From the results in Table 1, it can be known that the photoresist composition system using the phenolic hydroxyl-containing resin of the present invention has a high Tg and high solubility to a weakly alkaline developer.

[Positive Photosensitive Resin Composition] Embodiment 5, 6 Comparative example 3, 4 Dissolve 20 g of the phenolic hydroxyl-containing resin powder and 5 g of 1,2-diazonaphthoquinone (P-200: manufactured by Toyosei Co., Ltd.) powder shown in Table 2. A positive photosensitive resin composition was obtained in 75 g of propylene glycol monomethyl ether acetate (PGMEA).

The development contrast was evaluated for the positive-type photosensitive resin compositions obtained in Examples and Comparative Examples. The results are shown in Table 2. The development contrast system is set as follows: the alkali-soluble ADR1 and ADR2 (Å/s) of the photoresist resin composition (Example 3, 4 and Comparative Example 1, 2) without a photosensitive agent, and the positive photosensitive photosensitive agent prepared with a photosensitive agent. The ratio (ADR1/ADR3, ADR2/ADR4) of alkali-soluble ADR3 and ADR4 (Å/s) of the resin composition (embodiment 5, 6 and comparative example 3, 4). Among them, ADR3 and ADR4 are obtained in the same manner as ADR1 and ADR2, respectively. The evaluation system was set as described below. ○: Development contrast is 10 or more ×: Development contrast is less than 10

[Table 2] use resin Alkali solubility (Å/s) Development contrast Developer D-1: ADR3 Developer D-2: ADR4 ADR1/ADR3 ADR2/ADR4 Example 5 Example 1 320 10 〇(12) 〇(15) Example 6 Example 2 420 20 〇(11) 〇(11) Comparative example 3 Comparative Synthesis Example 1 570 10 ×(3) ×(3) Comparative example 4 Comparative Synthesis Example 2 30 10 〇(16) ×(1)

As can be seen from the results in Table 2, the positive-type photosensitive resin composition using the phenolic hydroxyl-containing resin of the present invention has a large effect of inhibiting dissolution due to the addition of a photosensitizer, so the affinity with the photosensitizer is high, so the sensitivity Also high.

none

Fig. 1 is the GPC spectrum of the resin containing phenolic hydroxyl group of embodiment 1. Fig. 2 is the ¹³ C-NMR spectrum of the resin containing phenolic hydroxyl group in Example 1. Fig. 3 is the GPC spectrum of the resin containing phenolic hydroxyl group of embodiment 2. Fig. 4 is the ¹³ C-NMR spectrum of the resin containing phenolic hydroxyl group in Example 2. FIG. 5 is a ¹³ C-NMR spectrum of the resin containing phenolic hydroxyl group in Comparative Synthesis Example 2. FIG.

none.

Claims (14)

A resin containing a phenolic hydroxyl group comprising: Structural unit (a) derived from a phenolic compound, Structural unit (b) derived from an aromatic aldehyde compound having a carboxyl group, and Structural unit (c) derived from an aromatic aldehyde compound. The resin containing phenolic hydroxyl groups as claimed in item 1, wherein the phenolic compound is a compound represented by the following formula (1): In formula (1), R ₁ is an aliphatic hydrocarbon group, an alkoxy group, an aryl group, an aralkyl group or a halogen atom; l is an integer from 0 to 2, and m is 1 or 2. The resin containing phenolic hydroxyl group as claimed in item 1 or 2, wherein the aromatic aldehyde compound having a carboxyl group is a compound represented by the following formula (2): In formula (2), R ₂ is a group selected from the group including aliphatic hydrocarbon group, alkoxy group, halogen atom, cyano group, and nitro group, and q is an integer of 0 to 4. As the resin containing phenolic hydroxyl group according to any one of claims 1 to 3, wherein the aromatic aldehyde compound is a compound represented by the following formula (3): In formula (3), R ₃ is a base selected from the group comprising aliphatic hydrocarbon group, alkoxy group, halogen atom, cyano group, and nitro group, n is an integer of 0 to 3, and p is 0 to 2 Integer of . As the resin containing phenolic hydroxyl group in any one of claims 1 to 4, wherein the molar ratio of the structural unit (a), structural unit (b) and structural unit (c) (structural unit (a): structural unit (b): Structural unit (c)) is 0.5 to 1.5: 0.05 to 1.0: 0.1 to 1.5. A photosensitive resin composition comprising the resin containing phenolic hydroxyl groups according to any one of claims 1 to 5, and a diazoquinone photosensitive agent. The photosensitive resin composition according to claim 6, which further comprises: a calix having a structural unit (a) derived from a phenolic compound and a structural unit (b) derived from an aromatic aldehyde compound having a carboxyl group Structure of phenolic resin. The photosensitive resin composition according to claim 6 or 7, wherein the diazoquinone-based photosensitive agent comprises a diazonaphthoquinone-based compound. A photoresist film obtained from the photosensitive resin composition according to any one of claims 6-8. A curable composition comprising the resin containing phenolic hydroxyl groups according to any one of claims 1 to 5, and a curing agent. A cured product of the curable composition according to claim 10. A method for manufacturing a photoresist pattern, comprising: A coating film forming step in which a coating film composed of the photosensitive resin composition according to any one of claims 6 to 8 is formed on a substrate, an exposing step of exposing the coating film, and A developing step of developing the coating film after the exposing step with a dilute weak alkaline developing solution. The method for manufacturing a photoresist pattern according to claim 12, wherein the pH of the dilute weak alkaline developing solution is not less than 8.0 and not more than 12.0. The method for producing a photoresist pattern according to claim 12 or 13, wherein the dilute weak alkaline developer is 0.1 to 10% by mass of an inorganic salt of an acid whose pKa is in the range of 6.0 to 12.0 in H ₂ O at 23°C aqueous solution.