JP6940834B2 - Phenolic hydroxyl group-containing resin, photosensitive composition, resist film, curable composition and cured product - Google Patents

Description

The present invention relates to phenolic hydroxyl group-containing resins, photosensitive compositions, resist films, curable compositions and cured products.

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. .. For example, a positive type resist using an alkali-soluble resin and a photosensitive agent such as a 1,2-naphthoquinonediazide compound as a resist used in manufacturing semiconductors such as ICs and LSIs, manufacturing display devices such as LCDs, and manufacturing original printing plates. Photoresist is known.

As the alkali-soluble resin, a positive photoresist composition using a cresol novolac type epoxy resin has been proposed (see, for example, Patent Documents 1 and 2).
The positive photoresist composition using the cresol novolac type epoxy resin was developed for the purpose of improving the developability such as sensitivity, but in recent years, the high integration of semiconductors has increased and the pattern has become thinner. There is a tendency, and better sensitivity is required. However, the positive photoresist composition using the cresol novolac type epoxy resin has a problem that sufficient sensitivity corresponding to thinning cannot be obtained. Further, since various heat treatments are performed in the manufacturing process of semiconductors and the like, higher heat resistance is also required, but a positive photoresist composition using a cresol novolac type epoxy resin has sufficient heat resistance. There was a problem that there was no.

Wafer level packaging technology is used to manufacture a patterned structure using a photoresist. Wafer level packaging technology is a mounting technology for manufacturing a semiconductor package by encapsulating, rewiring, and forming electrodes in the state of a wafer and separating them into individual pieces by dicing.

In wafer level packaging, an electrochemical deposition method is used for electronic wiring as the wiring density increases (see, for example, Non-Patent Document 1). Gold bumps, copper posts and copper wires used for repositioning wafer level packaging require a mold of resist to be electroplated. This resist layer is very thick as compared with the resist layer used in IC manufacturing. Both the size of the figure of the resist mold and the thickness of the resist layer are, for example, 2 μm to 100 μm, and it is necessary to pattern the photoresist with a high aspect ratio (resist thickness with respect to the line size).

For the patterning of photoresists with high aspect ratios, it has been proposed to use aliphatic polyaldehydes as nodules for metacresols or paracresols when synthesizing novolak resins (see, for example, Patent Document 3). However, there is a problem that it is difficult to achieve both heat resistance and alkali dissolution rate, which are important characteristics of a thick film resist.

Japanese Unexamined Patent Publication No. 2008-0881197 JP-A-2002-107925 Japanese Unexamined Patent Publication No. 9-6003

Gary Solomon, Electrochemically deposited solder bumps for wafer-level packaging, PACKAGING / ASSEMBLY, Solid State Technology, pages 83,84,86,88 April 2001

An object to be solved by the present invention is to provide a phenolic hydroxyl group-containing resin which has high heat resistance and exhibits excellent alkali developability when used as a resist material.

As a result of diligent studies to solve the above problems, the present inventors have made a reaction product of a triaryl compound containing a carboxyl group and an aliphatic aldehyde, and some or all of the carboxyl groups in the reaction product are present. We have found that the phenolic hydroxyl group-containing resin esterified with an alcohol compound is excellent in heat resistance and alkali developability, and completed the present invention.

That is, the present invention comprises a novolak-type phenol resin (C) and an alcohol compound (X) containing an aromatic compound (A) represented by the following formula (1) and an aliphatic aldehyde (B) as essential reaction raw materials. It relates to a phenolic hydroxyl group-containing resin which is a reaction product of.

（前記式（１）中、Ｒ_１及びＲ_２は、それぞれ独立に、炭素原子数１〜９の脂肪族炭化水素基、アルコキシ基、アリール基、アラルキル基又はハロゲン原子を表す。
ｍ、ｎ及びｐは、それぞれ独立に、０〜４の整数を表す。
Ｒ_１が複数ある場合、複数のＲ_１は互いに同じでも異なってもよい。
Ｒ_２が複数ある場合、複数のＲ_２は互いに同じでも異なってもよい。
Ｒ_３は、水素原子、炭素原子数１〜９の脂肪族炭化水素基、又は炭化水素基上にアルコキシ基、ハロゲン基及び水酸基から選択される置換基を１以上有する構造部位を表す。
Ｒ_４は、水酸基、炭素原子数１〜９の脂肪族炭化水素基、アルコキシ基又はハロゲン原子を表す。
Ｒ_４が複数ある場合、複数のＲ_４は互いに同じでも異なってもよい。）

(In the above 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 from 0 to 4.
When R ₁ is a plurality, the plurality of R ₁ may be the same or different.
When R ₂ are a plurality, the plurality of R ₂ may be the same or different.
R ₃ represents a structural site 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.
R ₄ represents a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group or a halogen atom.
If R ₄ is plural, R ₄ may be the same or different. )

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a phenolic hydroxyl group-containing resin having high heat resistance and exhibiting excellent alkali developability when used as a resist material.

It is a figure which shows the GPC chart of the carboxylic acid-containing phenolic trinuclear compound (A-1). It is a figure which shows ^{the 13} C-NMR chart of the carboxylic acid-containing phenolic trinuclear compound (A-1). It is a figure which shows the GPC chart of the novolak type phenol resin (C-1). It is a figure which shows ^{the 13} C-NMR chart of the novolak type phenol resin (C-1). It is a figure which shows the GPC chart of the esterified novolak type phenol resin (Z-1). It is a figure which shows ^{the 13} C-NMR chart of the esterified novolak type phenol resin (Z-1). It is a figure which shows the GPC chart of the esterified novolak type phenol resin (Z-2). It is a figure which shows ^{the 13} C-NMR chart of the esterified novolak type phenol resin (Z-2). It is a figure which shows the GPC chart of the esterified novolak type phenol resin (Z-3). It is a figure which shows ^{the 13} C-NMR chart of the esterified novolak type phenol resin (Z-3). It is a figure which shows the GPC chart of a novolak resin (C'-2). It is a figure which shows the GPC chart of a novolak resin (C'-3).

Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications as long as the effects of the present invention are not impaired.

[Phenolic hydroxyl group-containing resin]
The phenolic hydroxyl group-containing resin of the present invention is a novolak-type phenol resin (C) and an alcohol compound containing an aromatic compound (A) represented by the following formula (1) and an aliphatic aldehyde (B) as essential reaction raw materials. It is a reaction product with (X).

（前記式（１）中、Ｒ_１及びＲ_２は、それぞれ独立に、炭素原子数１〜９の脂肪族炭化水素基、アルコキシ基、アリール基、アラルキル基又はハロゲン原子を表す。
ｍ、ｎ及びｐは、それぞれ独立に、０〜４の整数を表す。
Ｒ_１が複数ある場合、複数のＲ_１は互いに同じでも異なってもよい。
Ｒ_２が複数ある場合、複数のＲ_２は互いに同じでも異なってもよい。
Ｒ_３は、水素原子、炭素原子数１〜９の脂肪族炭化水素基、又は炭化水素基上にアルコキシ基、ハロゲン基及び水酸基から選択される置換基を１以上有する構造部位を表す。
Ｒ_４は、水酸基、炭素原子数１〜９の脂肪族炭化水素基、アルコキシ基又はハロゲン原子を表す。
Ｒ_４が複数ある場合、複数のＲ_４は互いに同じでも異なってもよい。）

(In the above 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 from 0 to 4.
When R ₁ is a plurality, the plurality of R ₁ may be the same or different.
When R ₂ are a plurality, the plurality of R ₂ may be the same or different.
R ₃ represents a structural site 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.
R ₄ represents a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group or a halogen atom.
If R ₄ is plural, R ₄ may be the same or different. )

The phenolic hydroxyl group-containing resin of the present invention has a triarylmethane structure. The phenolic hydroxyl group-containing resin of the present invention has extremely high heat resistance because it contains the aromatic ring at a high density due to having the triarylmethane structure.
In the triarylmethane structure of the above formula (1), the two hydroxy groups and the carboxyl group are substituted with different aromatic rings, and a strong hydrogen bond is not formed. As a result, the phenolic hydroxyl group-containing resin of the present invention can maintain good proton dissociation property and can exhibit excellent alkali developability. Further, since some or all of the carboxyl groups in the triarylmethane structure are esterified by the reaction with the alcohol compound (X), the ester groups are extremely polar before and after hydrolysis (before and after the formation of the carboxyl group). It is possible to induce a change in the development and obtain a good development contrast.

[Novolak type phenol resin]
The novolak-type phenol resin (C) is a resin containing an aromatic compound (A) represented by the following formula (1) and an aliphatic aldehyde (B) as essential reaction raw materials.

（前記式（１）中、Ｒ_１及びＲ_２は、それぞれ独立に、炭素原子数１〜９の脂肪族炭化水素基、アルコキシ基、アリール基、アラルキル基又はハロゲン原子を表す。
ｍ、ｎ及びｐは、それぞれ独立に、０〜４の整数を表す。
Ｒ_１が複数ある場合、複数のＲ_１は互いに同じでも異なってもよい。
Ｒ_２が複数ある場合、複数のＲ_２は互いに同じでも異なってもよい。
Ｒ_３は、水素原子、炭素原子数１〜９の脂肪族炭化水素基、又は炭化水素基上にアルコキシ基、ハロゲン基及び水酸基から選択される置換基を１以上有する構造部位を表す。
Ｒ_４は、水酸基、炭素原子数１〜９の脂肪族炭化水素基、アルコキシ基又はハロゲン原子を表す。
Ｒ_４が複数ある場合、複数のＲ_４は互いに同じでも異なってもよい。）

(In the above 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 from 0 to 4.
When R ₁ is a plurality, the plurality of R ₁ may be the same or different.
When R ₂ are a plurality, the plurality of R ₂ may be the same or different.
R ₃ represents a structural site 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.
R ₄ represents a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group or a halogen atom.
If R ₄ is plural, R ₄ may be the same or different. )

In the above formula (1), _{the aliphatic hydrocarbon groups having 1 to 9 carbon atoms of R 1} , R ₂ , R ₃ and R ₄ include methyl group, ethyl group, propyl group, isopropyl group, butyl group and t. -Alkyl groups having 1 to 9 carbon atoms and cycloalkyl groups having 3 to 9 carbon atoms such as butyl group, hexyl group, cyclohexyl group, heptyl group, octyl group and nonyl group can be mentioned.

In the above 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 above formula (1), _{examples of the aryl group of R 1} and R ₂ include a phenyl group, a tolyl group, a xsilyl group, a naphthyl group, an anthryl group and the like.

In the above 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 above 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 formula (1), the R ₃ as "hydrocarbon groups on the alkoxy group, a substituent selected from halogen and hydroxyl groups structural moieties having 1 or more", a halogenated alkyl group, halogenated aryl group, 2 Examples thereof include an alkoxyalkoxy group such as a −methoxyethoxy group and a 2-ethoxyethoxy group, and an alkylalkoxy group substituted with a hydroxy group.

In the 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 R ₁ and the two R ₂ are independently alkyl groups having 1 to 3 carbon atoms. In this case, two R ₁ and two R ₂ are preferably each coupled to a 2,5-position of the phenolic hydroxyl group.

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

As the aromatic compound (A) represented by the formula (1), those having the same structure may be used alone, or a plurality of compounds having different molecular structures may be used.

The aromatic compound (A) represented by the formula (1) can be prepared, for example, by a condensation reaction between an alkyl-substituted phenol (a1) and an aromatic aldehyde (a2) having a carboxyl group.
The aromatic compound (A) represented by the formula (1) can be prepared, for example, by a condensation reaction between an alkyl-substituted phenol (a1) and an aromatic ketone (a3) having a carboxyl group.

The alkyl-substituted phenol (a1) is a phenol substituted with an alkyl group, and examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms, and a methyl group is preferable.
Specific examples of the alkyl-substituted phenol (a1) include o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, p-octylphenol, pt-butylphenol, o. Monoalkylphenols such as −cyclohexylphenol, m-cyclohexylphenol, and p-cyclohexylphenol; Alkylphenol; Examples thereof include trialkylphenols such as 2,3,5-trimethylphenol and 2,3,6-trimethylphenol. Among these, dialkylphenol is preferable, and 2,5-xylenol and 2,6-xylenol are more preferable.
The alkyl-substituted phenol (a1) may be used alone or in combination of two or more.

Examples of the aromatic aldehyde (a2) having a carboxyl group include compounds having a formyl group on the benzene ring such as benzene, phenol and resorcin, and compounds having an alkyl group, an alkoxy group, a halogen atom and the like in addition to the formyl group. ..
Specific examples of the aromatic aldehyde (a2) having a carboxyl group include 4-formylbenzoic acid, 2-formylbenzoic acid, 3-formylbenzoic acid, 4-formylbenzoate methyl, 4-formylbenzoate ethyl, 4-formylbenzoic acid. Propyl formil benzoate, isopropyl 4-formyl benzoate, butyl 4-formyl benzoate, isobutyl 4-formyl benzoate, tertiary butyl 4-formyl benzoate, cyclohexyl 4-formyl benzoate, tertiary octyl 4-formyl benzoate And so on. Of these, 4-formylbenzoic acid is preferable.
The aromatic aldehyde (a2) having a carboxyl group may be used alone or in combination of two or more.

The aromatic ketone (a3) having a carboxyl group is a compound having at least one carboxyl group and a carbonyl group on the aromatic ring.
Specific examples of the aromatic ketone (a3) having a carboxyl group include 2-acetylbenzoic acid, 3-acetylbenzoic acid, 4-acetylbenzoic acid, and methyl 2-acetylbenzoate and ethyl 2-acetylbenzoate. , 2-Acetylbenzoate propyl, 2-Acetylbenzoate isopropyl, 2-Acebenzoate butyl, 2-Acenatebenzoate isobutyl, 2-Acecbenzoate tertiary butyl, 2-Acetylbenzoate cyclohexyl, 2-Acetylbenzoic acid Examples include tertiary octyl. Of these, 2-acetylbenzoic acid and 4-acetylbenzoic acid are preferable.
The aromatic ketone (a3) may be used alone or in combination of two or more.

Specific examples of the aliphatic aldehyde (B) include formaldehyde, paraformaldehyde, 1,3,5-trioxane, acetaldehyde, propionaldehyde, tetraoxymethylene, polyoxymethylene, chloral, hexamethylenetetramine, glioxal, and n-butylaldehyde. , Caproaldehyde, allylaldehyde, crotonaldehyde, achlorine and the like.
The aliphatic aldehyde compound (B) may be used alone or in combination of two or more.

The aliphatic aldehyde (B) is preferably one or more selected from formaldehyde and paraformaldehyde, and formaldehyde is more preferable.
When formaldehyde and an aliphatic aldehyde other than formaldehyde are used as the aliphatic aldehyde (B), the amount of the aliphatic aldehyde other than formaldehyde used shall be in the range of 0.05 to 1 mol with respect to 1 mol of formaldehyde. Is preferable.

The method for producing the novolak type phenol resin (C) preferably includes the following three steps 1 to 3 (step 1).
Alkyl-substituted phenol (a1) and aromatic aldehyde (a2) having a carboxyl group are heated in the range of 60 to 140 ° C. in the presence of an acid catalyst, using a solvent as necessary, and polycondensed. Obtain the aromatic compound (A).
(Step 2)
The aromatic compound (A) obtained in step 1 is isolated from the reaction solution.
(Step 3)
The aromatic compound (A) and the aliphatic aldehyde (B) isolated in step 2 are heated in the range of 60 to 140 ° C. in the presence of an acid catalyst, if necessary, using a solvent, and polycondensed. To obtain a novolak type phenol resin (C).

Examples of the acid catalyst used in 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 paratoluenesulfonic acid are preferable in step 1, and sulfuric acid, oxalic acid and zinc acetate are preferable in 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 used in steps 1 and 3 as necessary include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,4-butane. Polycols such as diols, 1,5-pentanediols, 1,6-hexanediols, 1,7-heptanediols, 1,8-octanediols, 1,9-nonanediols, trimethylene glycols, diethylene glycols, polyethylene glycols and glycerins. 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether, etc. Glycol ethers; 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 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. Further, among these solvents, 2-ethoxyethanol is preferable from the viewpoint of excellent solubility of the obtained compound.

The charging ratio [(a1) / (a2)] of the alkyl-substituted phenol (a1) and the aromatic aldehyde (a2) having a carboxyl group in step 1 is the removability of the unreacted alkyl-substituted phenol (a1) and the product. The molar ratio is preferably in the range of 1 / 0.2 to 1 / 0.5, and more preferably in the range of 1 / 0.25 to 1 / 0.45, because the yield and the purity of the reaction product are excellent.

The charging ratio [(A) / (B)] of the aromatic compound (A) and the aliphatic aldehyde (B) in step 3 can suppress excessive high molecular weight (gelation) and is suitable as a phenol resin for resist. Since a product having a high molecular weight can be obtained, the molar ratio is preferably in the range of 1 / 0.5 to 1 / 1.2, and more preferably in the range of 1 / 0.6 to 1 / 0.9.

As a method for isolating the aromatic compound (A) from the reaction solution in 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. Is dissolved in a solvent (S2) that dissolves the reaction product and is also mixed with the poor solvent (S1), and is put into the poor solvent (S1) again to filter out the resulting precipitate. Be done.
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. On the other hand, 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-. Polyols such as pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin; 2-ethoxyethanol, Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether; 1, Cyclic ethers such as 3-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 steps 1 and 3, the aromatic compound (A) produced by the reaction dissolves in the solvent when heated at 80 ° C. or higher. Since the crystals of the aromatic compound (A) are precipitated by cooling as it is, the aromatic compound (A) can be isolated by filtering the crystals. In this case, it is not necessary to use the poor solvent (S1) and the solvent (S2).

The aromatic compound (A) represented by the formula (1) can be obtained by the isolation method of the above 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. Is particularly preferred. The purity of the aromatic compound (A) can be determined from the area ratio of the GPC chart, and is measured under the measurement conditions described later.

The weight average molecular weight (Mw) of the novolak-type phenol resin (C) is preferably in the range of 2,000 to 35,000, more preferably in the range of 2,000 to 25,000.
The weight average molecular weight (Mw) of the novolak-type phenol resin (C) was measured by gel permeation chromatography (hereinafter abbreviated as "GPC") under the following measurement conditions.

(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 velocity: 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

[Alcohol compound (X)]
The phenolic hydroxyl group-containing resin of the present invention is a reaction product of a novolak-type phenol resin (C) and an alcohol compound (X). Here, the reaction between the novolak-type phenol resin (C) and the alcohol compound (X) is, for example, a dehydration esterification reaction.

Examples of the alcohol compound (X) include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, propylene glycol, trimethyl propane and the like. 10 or less aliphatic alcohols; aromatic alcohols with 10 or less carbon atoms such as benzyl alcohol; 2-methoxyethyl alcohol, 2-ethoxyethyl alcohol, 1-methoxy-2-propyl alcohol, 1-ethoxy-2-propyl alcohol , 3-methoxy-1-butyl alcohol, 2-isopropoxyethyl alcohol and other ether alcohols containing ether bonds and having 10 or less carbon atoms; and 3-hydroxy-2-butanone and other ketone groups containing 10 or less carbon atoms. Ketoalcohols; ester alcohols having 10 or less carbon atoms containing an ester group such as methyl hydroxyisobutyrate and the like can be mentioned. Of these, aliphatic alcohols having 10 or less carbon atoms and ether alcohols having 10 or less carbon atoms are preferable, and ethyl alcohols, n-propyl alcohols, isopropyl alcohols (2-propanol), n-butyl alcohols, and isobutyl alcohols (2). -Methyl-2-propanol), t-butyl alcohol and 2-ethoxyethyl alcohol (2-ethoxyethanol) are more preferred.
The alcohol compound (X) may be used alone or in combination of two or more.

The dehydration esterification reaction can be carried out by stirring a mixture of the novolak type phenol resin (C) and the alcohol compound (X) in the presence of an acid catalyst.
Examples of the acid catalyst 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.
The reaction temperature is not particularly limited, but is preferably in the range of, for example, 10 ° C to 60 ° C, and room temperature is preferable because no special equipment is required.

The dehydration esterification reaction between the novolak-type phenol resin (C) and the alcohol compound (X) is carried out with the carboxyl group in the novolak-type phenol resin (C) derived from the aromatic compound (A) represented by the above formula (1). The alcohol compound (X) reacts to form an ester bond with dehydration.
The charging ratio of the novolak-type phenol resin (C) and the alcohol compound (X) in the dehydration esterification reaction is not particularly limited, but is, for example, phenol resin / alcohol = 1 / 0.5 to 1/10 by weight. ..

The phenolic hydroxyl group-containing resin of the present invention is a resin containing a structure in which some or all of the carboxyl groups of the novolak-type phenol resin (C) are esterified, and the esterification rate of the carboxyl groups of the novolak-type phenol resin (C). Is preferably 5 to 90 mol%, more preferably 10 to 85 mol% or 5 to 70 mol%.
The esterification rate of the phenolic hydroxyl group-containing resin of the present invention is confirmed by the method described in Examples.

The number average molecular weight (Mn) of the phenolic hydroxyl group-containing resin of the present invention is preferably in the range of 500 to 7,000, more preferably in the range of 1,000 to 5,000.
The weight average molecular weight (Mw) of the phenolic hydroxyl group-containing resin of the present invention is preferably in the range of 3,000 to 20,000, more preferably in the range of 5,000 to 15,000.
The number average molecular weight and the weight average molecular weight of the phenolic hydroxyl group-containing resin of the present invention are the same as those of the novolak type phenol resin (C) and are measured by gel permeation chromatography (hereinafter abbreviated as "GPC").

[Photosensitive composition]
The photosensitive composition of the present invention contains the phenolic hydroxyl group-containing resin of the present invention and a photoacid generator.
The photoacid generator is not particularly limited, and known photoacid generators can be used, and examples thereof include organic halogen compounds, sulfonic acid esters, onium salts, diazonium salts, and disulfon compounds.

Specific examples of the photoacid generator include the following.
Tris (trichloromethyl) -s-triazine, tris (tribromomethyl) -s-triazine, tris (dibromomethyl) -s-triazine, 2,4-bis (tribromomethyl) -6-p-methoxyphenyl-s -Haloalkyl group-containing s-triazine derivatives such as -triazine, (2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine);

Halogen-substituted paraffin hydrocarbon compounds such as 1,2,3,4-tetrabromoethane, 1,1,2,2-tetrabromoethane, carbon tetrabromide, iodoform; hexabromocyclohexane, hexachlorocyclohexane, hexabromocyclo Halogen-substituted cyclopara-paraffin hydrocarbon compounds such as dodecane;

Haloalkyl group-containing benzene derivatives such as bis (trichloromethyl) benzene and bis (tribromomethyl) benzene; haloalkyl group-containing sulfone compounds such as tribromomethylphenyl sulfone and trichloromethylphenyl sulfone; halogen-containing compounds such as 2,3-dibromosulfolane Sulfolane compounds; haloalkyl group-containing isocyanurate compounds such as tris (2,3-dibromopropyl) isocyanurate;

Triphenylsulfonium chloride, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroarce Sulfonium salts such as nate, triphenylsulfonium hexafluorophosphonate;

Iodonium salts such as diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphonate;

Methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, phenyl p-toluenesulfonate, 1,2,3-tris (p-toluenesulfonyloxy) benzene, benzoin p-toluenesulfonate Estel, methyl methanesulphonate, ethyl methanesulphonate, butyl methanesulphonate, 1,2,3-tris (methanesulfonyloxy) benzene, phenyl methanesulphonate, benzoinate methanesulphonate, methyl trifluoromethanesulphonate, trifluoromethane Sulfonic acid ester compounds such as ethyl sulfonate, butyl trifluoromethanesulfonate, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, phenyl trifluoromethanesulfonate, benzoin ester of trifluoromethanesulfonic acid; disulfon compounds such as diphenyldisulfone ;

Bis (phenylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, cyclohexylsulfonyl- (2-methoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (3-methoxyphenylsulfonyl) diazomethane, Cyclohexylsulfonyl- (4-methoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2-methoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (3-methoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (4-methoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl -(2-Fluorophenylsulfonyl) diazomethane, cyclohexylsulfonyl- (3-fluorophenylsulfonyl) diazomethane, cyclohexylsulfonyl- (4-fluorophenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2-fluorophenylsulfonyl) diazomethane, cyclopentylsulfonyl- ( 3-Fluorophenylsulfonyl) diazomethane, cyclopentylsulfonyl- (4-fluorophenylsulfonyl) diazomethane, cyclohexylsulfonyl- (2-chlorophenylsulfonyl) diazomethane, cyclohexylsulfonyl- (3-chlorophenylsulfonyl) diazomethane, cyclohexylsulfonyl- (4-chlorophenylsulfonyl) ) Diazomethane, cyclopentylsulfonyl- (2-chlorophenylsulfonyl) diazomethane, cyclopentylsulfonyl- (3-chlorophenylsulfonyl) diazomethane, cyclopentylsulfonyl- (4-chlorophenylsulfonyl) diazomethane, cyclohexylsulfonyl- (2-trifluoromethylphenylsulfonyl) diazomethane, Cyclohexylsulfonyl- (3-trifluoromethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (4-trifluoromethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2-trifluoromethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (3-trifluoro) Methylphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (4-trifluoromethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (2-to Rifluoromethoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (3-trifluoromethoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (4-trifluoromethoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2-trifluoromethoxyphenylsulfonyl) diazomethane, Cyclopentylsulfonyl- (3-trifluoromethoxyphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (4-trifluoromethoxyphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (2,4,6-trimethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (2,2) 3,4-trimethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (2,4,6-triethylphenylsulfonyl) diazomethane, cyclohexylsulfonyl- (2,3,4-triethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2,4) 6-trimethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2,3,4-trimethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2,4,6-triethylphenylsulfonyl) diazomethane, cyclopentylsulfonyl- (2,3,4- Triethylphenylsulfonyl) diazomethane, phenylsulfonyl- (2-methoxyphenylsulfonyl) diazomethane, phenylsulfonyl- (3-methoxyphenylsulfonyl) diazomethane, phenylsulfonyl- (4-methoxyphenylsulfonyl) diazomethane, bis (2-methoxyphenylsulfonyl) Diazomethane, bis (3-methoxyphenylsulfonyl) diazomethane, bis (4-methoxyphenylsulfonyl) diazomethane, phenylsulfonyl- (2,4,6-trimethylphenylsulfonyl) diazomethane, phenylsulfonyl- (2,3,4-trimethylphenyl) Sulfonyl) diazomethane, phenylsulfonyl- (2,4,6-triethylphenylsulfonyl) diazomethane, phenylsulfonyl- (2,3,4-triethylphenylsulfonyl) diazomethane, 2,4-dimethylphenylsulfonyl- (2,4,6) -Trimethylphenylsulfonyl) diazomethane, 2,4-dimethylphenylsulfonyl- (2,3,4-trimethylphenylsulfonyl) Sulfonyl diazide compounds such as diazomethane, phenylsulfonyl- (2-fluorophenylsulfonyl) diazomethane, phenylsulfonyl- (3-fluorophenylsulfonyl) diazomethane, phenylsulfonyl- (4-fluorophenylsulfonyl) diazomethane;

O-nitrobenzyl ester compounds such as o-nitrobenzyl-p-toluenesulfonate;

Sulfone hydrazide compounds such as N, N'-di (phenylsulfonyl) hydrazide;

A sulfonium salt which is a salt of a sulfonium cation such as triaryl sulfonium and triaralkyl sulfonium and a sulfonate such as fluoroalkane sulfonate, arene sulfonate and alkane sulfonate;

An iodonium salt which is a salt of an iodonium cation such as diallyl iodonium and a sulfonate such as fluoroalkane sulfonate, arene sulfonate, or alkane sulfonate;

Bissulfonyldiazomethane compounds such as bis (alkylsulfonyl) diazomethane, bis (cycloalkylsulfonyl) diazomethane, bis (perfluoroalkylsulfonyl) diazomethane, bis (arylsulfonyl) diazomethane, bis (aralkylsulfonyl) diazomethane;

An N-sulfonyloxyimide compound consisting of a combination of a dicarboxylic acid imide compound and a sulfonate such as fluoroalkane sulfonate, arene sulfonate, or alkane sulfonate;

Benzoin sulfonate compounds such as benzointosilate, benzoin mesylate, benzoin butane sulfonate;

A polyhydroxyarene sulfonate compound in which all the hydroxy groups of the polyhydroxyarene compound are replaced with a sulfonate such as fluoroalkanes sulfonate, arene sulfonate, or alkane sulfonate;

Nitrobenzyl sulfonate compounds such as fluoroalkane sulfonic acid (poly) nitrobenzyl, allene sulfonic acid (poly) nitrobenzyl, alkane sulfonic acid (poly) nitrobenzyl;
Fluoroalkanebenzyl sulfonate compounds such as fluoroalkanesulfonic acid (poly) fluoroalkanebenzyl, allenesulfonic acid (poly) fluoroalkanebenzyl, alkanesulfonic acid (poly)fluoroalkanebenzyl;

Bis (arylsulfonyl) alkane compound;

Bis-O- (arylsulfonyl) -α-dialkylglycime, bis-O- (arylsulfonyl) -α-dicycloalkylglioxime, bis-O- (arylsulfonyl) -α-diarylglioxime, bis-O -(Alkylsulfonyl) -α-dialkylglioxime, bis-O- (alkylsulfonyl) -α-dicycloalkylglioxime, bis-O- (alkylsulfonyl) -α-diarylglycime, bis-O- (fluoro) Alkylsulfonyl) -α-dialkylglioxime, bis-O- (fluoroalkylsulfonyl) -α-dicycloalkylglioxime, bis-O- (fluoroalkylsulfonyl) -α-diarylglycime, bis-O- (aryl) Sulfonyl) -α-dialkylnioxime, bis-O- (arylsulfonyl) -α-dicycloalkylnioxime, bis-O- (arylsulfonyl) -α-diarylnioxime, bis-O- (alkylsulfonyl)- α-Dialkylnioxime, bis-O- (alkylsulfonyl) -α-dicycloalkylnioxime, bis-O- (alkylsulfonyl) -α-diarylnioxime, bis-O- (fluoroalkylsulfonyl) -α- Oxime compounds such as dialkylnioxime, bis-O- (fluoroalkylsulfonyl) -α-dicycloalkylnioxime, bis-O- (fluoroalkylsulfonyl) -α-diarylnioxime;

Alylsulfonyloxyiminoaryl acetonitrile, alkylsulfonyloxyiminoaryl acetonitrile, fluoroalkylsulfonyloxyiminoaryl acetonitrile, ((arylsulfonyl) oxyimino-thiophene-iriden) arylnitrile, ((alkylsulfonyl) oxyimino-thiophene-iriden) arylnitrile, ((Fluoroalkylsulfonyl) oxyimino-thiophene-iriden) aryl acetonitrile, bis (arylsulfonyloxyimino) allyligen acetonitrile, bis (alkylsulfonyloxyimine) allylrange acetonitrile, bis (fluoroalkylsulfonyloxyimino) allylrange acetonitrile, aryl Modified oxime compounds such as fluoroalkanone-O- (alkylsulfonyl) oxime, arylfluoroalkanone-O- (arylsulfonyl) oxime, and arylfluoroalkanone-O- (fluoroalkylsulfonyl) oxime.

The photoacid generator may be used alone or in combination of two or more.
The content of the photoacid generator in the photosensitive composition of the present invention is, for example, in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin solid content in the photosensitive composition, and is preferable. The range is 0.1 parts by mass to 10 parts by mass.
When the content of the photoacid generator is in the above range, the photosensitive composition of the present invention can be a photosensitive composition having high photosensitivity.

The photosensitive composition of the present invention may contain the phenolic hydroxyl group-containing resin of the present invention and the photoacid generator, and may optionally contain other components.
Examples of the other components include organic base compounds, other resins other than the phenolic hydroxyl group-containing resin of the present invention, photosensitizers, surfactants, dyes, fillers, cross-linking agents, dissolution accelerators and the like.

The photosensitive composition of the present invention may contain an organic base compound for neutralizing the acid generated from the photoacid generator at the time of exposure. When the photosensitive composition of the present invention contains the organic base compound, an effect of preventing dimensional fluctuation of the resist pattern due to the movement of the acid generated from the photoacid generator can be obtained.

Specific examples of the organic base compound include pyrimidine, (poly) aminopyrimidine, (poly) hydroxypyrimidine, (poly) amino (poly) hydroxypyrimidine, (poly) amino (poly) alkylpyrimidine, and (poly) amino (poly). ) Pyrimidine compounds such as alkoxypyrimidine, (poly) hydroxy (poly) alkylpyrimidine, (poly) hydroxy (poly) alkoxypyrimidine; pyridine compounds such as pyridine, (poly) alkylpyridine, dialkylaminopyridine; polyalkanolamines, tri () Examples thereof include hydroxyalkyl group-containing amine compounds such as hydroxyalkyl) aminoalkane and bis (hydroxyalkyl) iminotris (hydroxyalkyl) alkane; and aminoaryl compounds such as aminophenol.
The organic base compound may be used alone or in combination of two or more.

The content of the organic base compound in the photosensitive composition of the present invention is preferably in the range of 0.1 to 100 mol%, preferably 1 to 50 mol%, based on 1 mol of the photoacid generator. More preferably, it is in the range.

The photosensitive composition of the present invention may contain other resins other than the phenolic hydroxyl group-containing resin of the present invention.
The other resin is not particularly limited, and is, for example, a resin soluble in an alkaline developer or a resin that dissolves in an alkaline developer when used in combination with an additive such as a photoacid generator.

Examples of the other resin include phenolic resins other than the phenolic hydroxyl group-containing resin of the present invention; p-hydroxystyrene, p- (1,1,1,3,3,3-hexafluoro-2-hydroxypropyl) styrene and the like. Polypolymer or copolymer of the hydroxy group-containing styrene compound; the hydroxyl group of the phenol resin or the polymer of the hydroxy group-containing styrene compound was modified with an acid-degradable group such as a t-butoxycarbonyl group or a benzyloxycarbonyl group. Resins; homopolymers or copolymers of (meth) acrylic acid; alternating polymers of alicyclic polymerizable monomers such as norbornene compounds and tetracyclododecene compounds with maleic anhydride or maleimide.

Specific examples of the phenol resin other than the phenolic hydroxyl group-containing resin of the present invention include a phenol novolac resin, a cresol novolac resin, a naphthol novolac resin, a co-condensed novolak resin using various phenolic compounds, and an aromatic hydrocarbon formaldehyde resin. Modified phenol resin, dicyclopentadienephenol addition type resin, phenol aralkyl resin (Zyroc resin), naphthol aralkyl resin, trimethylolmethane resin, tetraphenylol ethane resin, biphenyl modified phenol resin (polyphenol nuclei linked by bismethylene group) Phenolic phenol compounds), biphenyl-modified naphthol resins (polyvalent naphthol compounds in which phenol nuclei are linked by bismethylene groups), aminotriazine-modified phenol resins (polyphenol compounds in which phenol nuclei are linked by melamine, benzoguanamine, etc.) and alkoxy groups. Examples thereof include phenol resins such as a contained aromatic ring-modified novolak resin (a polyhydric phenol compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).

Among the specific examples of the phenol resin other than the phenolic hydroxyl group-containing resin of the present invention, since it is a photosensitive composition having an excellent balance of developability, heat resistance and fluidity, it is a cresol novolac resin, and cresol and other phenols. A co-condensed novolak resin with a sex compound is preferable.
Cresol novolak resin or co-condensed novolak resin of cresol and other phenolic compounds, specifically, an essential reaction of one or more cresol and aldehyde compound selected from o-cresol, m-cresol and p-cresol. It is a novolak resin obtained by using it as a raw material and appropriately using other phenolic compounds in combination.

The other resins may be used alone or in combination of two or more.
The content of the other resin in the photosensitive composition of the present invention is not particularly limited and may be arbitrarily set according to a desired application. For example, the proportion of the phenolic hydroxyl group-containing resin of the present invention in the total of the resin components in the photosensitive composition of the present invention may be set to be 60% by mass or more, preferably 80% by mass or more.

The photosensitive composition of the present invention may contain a photosensitive agent usually used as a resist material. The photosensitizer 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 is meant to include a partial ester compound, and the amidate is meant 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- [2- (4-hydroxyphenyl) -2-propyl] 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) Tris (hydroxyphenyl) methane compounds such as phenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane or methyl substituents thereof;
Bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -4- Hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) 5-Cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-3) 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- A bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methane compound such as 4-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane, or a compound thereof. Examples include methyl substituents.

The photosensitizer may be used alone or in combination of two or more.
Since the content of the photosensitive agent in the photosensitive composition of the present invention is a photosensitive composition having excellent photosensitivity, it is 5 to 50 with respect to a total of 100 parts by mass of the resin component of the photosensitive composition of the present invention. It is preferably parts by mass.

The photosensitive composition of the present invention may contain a surfactant. When the photosensitive composition of the present invention contains a surfactant, effects such as improvement of film forming property and pattern adhesion and reduction of development defects when the photosensitive composition of the present invention is used for resist applications. Is obtained.
As the surfactant, a known surfactant can be used. Examples of the surfactant include nonionic surfactants, fluorine-based surfactants, silicone-based surfactants and the like.

The surfactant may be used alone or in combination of two or more.
The content of the surfactant in the photosensitive composition of the present invention is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass in total of the resin components of the photosensitive composition of the present invention.

The photosensitive composition of the present invention is preferably in a state in which the phenolic hydroxyl group-containing resin of the present invention is dissolved in an organic solvent.
Examples of the organic solvent include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether propylene glycol monomethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol di. Dialkylene glycol dialkyl ethers such as propyl ether and diethylene glycol dibutyl ether; alkylene glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate; acetone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone and the like. Ketone compounds; cyclic ethers such as dioxane; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2-hydroxy-3- Examples thereof include ester compounds such as methyl methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate and ethyl acetoacetate.

The organic solvent may be used alone or in combination of two or more.
The content of the organic solvent in the photosensitive composition of the present invention is not particularly limited, and for example, it may be set to an amount capable of dissolving all the phenolic hydroxyl group-containing resin of the present invention in the photosensitive composition.

The photosensitive composition of the present invention can be produced by blending each of the above components and mixing them using a stirrer or the like. When the photosensitive composition of the present invention contains a filler or a pigment, it can be produced by dispersing or mixing using a disperser such as a dissolver, a homogenizer, or a three-roll mill.

The photosensitive composition of the present invention can be used as a resist material.
When the photosensitive composition of the present invention is used as a resist material, the photosensitive composition of the present invention may be used as it is as a coating material, or the photosensitive composition of the present invention may be applied onto a support film to obtain a product. The coating film may be removed from the solvent to form a resist film.
Examples of the support film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. The support film may be a single-layer film or a laminated film composed of a plurality of films. Further, the surface of the support film may be corona-treated or coated with a release agent.

Examples of general photolithography methods using the photosensitive composition of the present invention include the following methods.
First, the photosensitive composition of the present invention is applied onto a photolithographic object such as a silicon substrate, a silicon carbide substrate, or a gallium nitride substrate, and prebaked under a temperature condition of 60 to 150 ° C. The coating method at this time may be any method such as spin coating, roll coating, flow coating, dip coating, spray coating, and doctor blade coating. Then, the resist pattern is formed by exposing through the resist pattern and developing with an alkaline developer.

When the photosensitive composition of the present invention is used for a permanent resist film, it may contain a cross-linking agent.
Examples of the cross-linking agent include those similar to the curing agent contained in the curable composition described later.
The cross-linking agent may be used alone or in combination of two or more.

Examples of the method for forming the resist permanent film include the following methods.
First, the photosensitive composition of the present invention is applied onto an object to be photolithographically subjected to, such as a silicon substrate, a silicon carbide substrate, and a gallium nitride substrate, and prebaked under a temperature condition of 60 to 150 ° C. The coating method is the same as that mentioned above. Next, the resist pattern is formed by exposing through the resist pattern, further thermosetting at a temperature of 110 to 210 ° C., and then developing with an alkaline developer. Alternatively, after exposure, it may be first developed with an alkaline developer and then thermoset at a temperature condition of 110 to 210 ° C.

Specific examples of the resist permanent film include a solder resist, a package material, an underfill material, a package adhesive layer of a circuit element, an adhesive layer between a product circuit element and a circuit board, and the like in a semiconductor device. Further, in a thin display typified by LCD and OELD, a thin film transistor protective film, a liquid crystal color filter protective film, a black matrix, a spacer and the like can be mentioned.

[Curable composition]
The curable composition of the present invention contains the phenolic hydroxyl group-containing resin of the present invention and a curing agent.
The curing agent 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. Examples thereof include compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, acid anhydrides, and oxazoline compounds.

Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, and hexamethylol melamine, which are compounds in which 1 to 6 methylol groups are methoxymethylated, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, and hexamethylol melamine. Examples thereof include compounds in which 1 to 6 methylol groups are acyloxymethylated.

Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, tetramethoxymethylbenzoguanamine, a compound in which 1 to 4 methylol groups of tetramethylol guanamine are methoxymethylated, tetramethoxyethyl guanamine, tetraacyloxyguanamine, and the like. Examples thereof include compounds in which 1 to 4 methylol groups of tetramethylolguanamine are acyloxymethylated.

Examples of the glycol uryl compound include 1,3,4,6-tetrakis (methoxymethyl) glycol uryl, 1,3,4,6-tetrakis (butoxymethyl) glycol uryl, and 1,3,4,6-tetrakis. (Hydroxymethyl) glycol uryl and the like can be mentioned.

Examples of the urea compound include 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea and 1,1,3,3-tetrakis (methoxymethyl) urea. Can be mentioned.

Examples of the resole resin include phenol, alkylphenols such as cresol and xylenol, phenylphenol, resorcinol, biphenyl, bisphenol such as bisphenol A and bisphenol F, phenolic hydroxyl group-containing compounds such as naphthol and dihydroxynaphthalene, and aldehyde compounds. Examples thereof include a polymer obtained by reacting under alkaline catalytic conditions.

Examples of the epoxy compound include diglycidyloxynaphthalene, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, and naphthol-cresol co-condensed novolac type epoxy resin. , Phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane, naphthylene ether type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene -Pharmon-added reaction type epoxy resin, phosphorus atom-containing epoxy resin, polyglycidyl ether which is a cocondensate of a phenolic hydroxyl group-containing compound and an alkoxy group-containing aromatic compound, and the like can be mentioned.

Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate and the like.

Examples of the azide compound include 1,1'-biphenyl-4,4'-bis azide, 4,4'-methylidene azide, 4,4'-oxybis azide and the like.

Examples of the compound containing a double bond such as an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, and tetramethylene glycol di. Vinyl ether, neopentyl glycol divinyl ether, trimethylpropan trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetra Examples thereof include vinyl ether, sorbitol pentavinyl ether, trimethyl propan trivinyl ether and the like.

Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, 4 Aromatic acid anhydrides such as 4'-(isopropyridene) diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrochloride Examples thereof include alicyclic carboxylic acid anhydrides such as phthalic acid, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, and trialkyltetrahydrophthalic anhydride.

Among the above-mentioned curing agents, glycol uryl compounds, urea compounds, and resol resins are preferable, and glycol uryl compounds are more preferable, because a cured product having high curability and excellent heat resistance can be obtained.

The curing agent may be used alone or in combination of two or more.
The content of the curing agent in the curable composition of the present invention is preferably 0.5 to 50 parts by mass with respect to 100 parts by mass in total of the resin components of the curable composition of the present invention.

The curable composition of the present invention may contain the phenolic hydroxyl group-containing resin and the curing agent of the present invention, and may optionally contain other components.
Examples of the other components include other resins other than the phenolic hydroxyl group-containing resin of the present invention, curing accelerators, surfactants, dyes, fillers, cross-linking agents, dissolution accelerators and the like.

The curable composition of the present invention may contain other resins other than the phenolic hydroxyl group-containing resin of the present invention.
Examples of the other resin include an addition polymer resin of an alicyclic diene compound such as novolak resin and dicyclopentadiene and a phenol compound, a modified novolak resin of a phenolic hydroxyl group-containing compound and an alkoxy group-containing aromatic compound, and phenol. Examples thereof include aralkyl resin (Zyroc resin), naphthol aralkyl resin, trimethylolmethane resin, tetraphenylol ethane resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, aminotriazine-modified phenol resin, vinyl polymer and the like.

Specific examples of the novolak resin include alkylphenols such as phenol, cresol and xylenol, phenylphenols, resorcinol, biphenyl, bisphenols such as bisphenol A and bisphenol F, phenolic hydroxyl group-containing compounds such as naphthol and dihydroxynaphthalene, and aldehyde compounds. Examples thereof include a polymer obtained by reacting the above under acid-catalyzed conditions.

Specific examples of the vinyl polymer include polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaftylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, and the like. Examples thereof include homopolymers of vinyl compounds such as poly (meth) acrylate, and copolymers thereof.

The other resins may be used alone or in combination of two or more.
The content of the other resin in the curable composition of the present invention is not particularly limited and may be arbitrarily set according to a desired application. For example, it is preferable that the amount of the other resin is 0.5 to 100 parts by mass with respect to 100 parts by mass of the phenolic hydroxyl group-containing resin of the present invention contained in the curable composition of the present invention.

The curable composition of the present invention may contain a curing accelerator.
Specific examples of the curing accelerator include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenol sulfonic acid, paratoluene sulfonic acid, zinc acetate, manganese acetate, and the above-mentioned photoacid generator.

The curing accelerator may be used alone or in combination of two or more.
The content of the curing accelerator in the curable composition of the present invention is not particularly limited, and is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin solid content of the curable composition of the present invention. ..

The curable composition of the present invention is preferably in a state in which the phenolic hydroxyl group-containing resin of the present invention is dissolved in an organic solvent.
Examples of the organic solvent include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether propylene glycol monomethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol di. Dialkylene glycol dialkyl ethers such as propyl ether and diethylene glycol dibutyl ether; alkylene glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate; acetone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone and the like. Ketone compounds; cyclic ethers such as dioxane; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2-hydroxy-3- Examples thereof include ester compounds such as methyl methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate and ethyl acetoacetate.

The organic solvent may be used alone or in combination of two or more.
The content of the organic solvent in the curable composition of the present invention is not particularly limited, and for example, it may be set to an amount capable of dissolving all the phenolic hydroxyl group-containing resin of the present invention in the curable composition.

The curable composition of the present invention can be produced by blending each of the above components and mixing them using a stirrer or the like. When the curable composition of the present invention contains a filler or a pigment, it can be produced by dispersing or mixing using a disperser such as a dissolver, a homogenizer, or a three-roll mill.

The curable composition of the present invention can be used as a resist material, and the cured product of the curable composition of the present invention can be used as a resist.
When the curable composition of the present invention is used as a resist material, the curable composition of the present invention may be used as it is as a coating material, or the curable composition of the present invention may be applied onto a support film to obtain the result. The coating film may be removed from the solvent to form a resist film.
Examples of the support film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. The support film may be a single-layer film or a laminated film composed of a plurality of films. Further, the surface of the support film may be corona-treated or coated with a release agent.

When the curable composition of the present invention is used for a resist underlayer film, examples of a method for producing a resist underlayer film include the following.
The curable composition of the present invention is applied onto a silicon substrate, a silicon carbide substrate, a gallium nitride substrate, or the like to be subjected to photolithography, dried under a temperature condition of 100 to 200 ° C., and then further heated to 250 to 400 ° C. A resist underlayer film is formed by a method such as heating and curing under temperature conditions. Next, a resist pattern is formed on the underlayer film by a normal photolithography operation, and a resist pattern is formed by a multilayer resist method by dry etching with a halogen-based plasma gas or the like.

The curing method of the curable composition of the present invention is not particularly limited, and it can be cured by an appropriate method such as thermosetting or photocuring depending on the type of curing agent, the type of curing accelerator, and the like. Curing conditions such as the heating temperature and time in thermosetting, the type of light rays in photocuring, and the exposure time are appropriately adjusted according to the type of curing agent, the type of curing accelerator, and the like.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
The number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity (Mw / Mn) of the resins prepared in the examples were measured under the following GPC measurement conditions.
[GPC measurement conditions]
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation
Column: Showa Denko KK "Shodex KF802" (8.0 mm Ф x 300 mm) + Showa Denko KK "Shodex KF802" (8.0 mm Ф x 300 mm) + Showa Denko KK "Shodex KF803" (8.0 mm Ф x) 300mm) + "Shodex KF804" manufactured by Showa Denko KK (8.0mm Ф x 300mm)
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 velocity: 1.0 mL / min Sample: A solution obtained by filtering 0.5% by mass of a tetrahydrofuran solution in terms of resin solid content with a microfilter Injection amount: 0.1 mL
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

The measurement of ¹³ C-NMR spectrum in the examples, using a Nippon Denshi Co. "AL-400", a structural analysis was performed by analyzing the _{DMSO-d 6} solution of the sample. The measurement conditions of the ¹³ C-NMR spectrum are shown below.
[ ¹³ C-NMR spectrum measurement conditions]
Measurement mode: SGNNE (1H complete decoupling method for NOE elimination)
Pulse angle: 45 ° C Pulse sample concentration: 30 wt%
Accumulation number: 10,000 times

Synthesis Example 1 Synthesis of carboxylic acid-containing phenolic trinuclear compound 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 equipped with a cooling tube. It was 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 completion of 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 283 g of a pale pink crystal precursor compound (A-1). ..

^{As a result of 13} C-NMR spectrum measurement of the obtained precursor compound (A-1), it was confirmed that the compound was represented by the following structural formula. The GPC purity calculated from the GPC chart was 97.9%. The GPC chart of the precursor compound (A-1) is shown in FIG. 1, and the ¹³ C-NMR chart is shown in FIG.

Production Example 1 Synthesis of carboxylic acid-containing novolak-type phenol resin After charging 188 g of the precursor compound (A-1) and 16 g of 92% paraformaldehyde (B-1) into a 1000 ml 4-port flask equipped with a cooling tube, 500 ml of acetic acid. Was dissolved in. After adding 10 ml of sulfuric acid while cooling in an ice bath, the mixture was heated to 80 ° C. in an oil bath and reacted with stirring for 4 hours. After completion of the reaction, water was added to the obtained solution to reprecipitate the crude product. The crude product was redissolved in acetone and then reprecipitated with water, and then the precipitate was filtered off and vacuum dried to obtain 182 g of an orange powder novolak-type phenol resin (C-1).
The obtained novolak-type phenol resin (C-1) had a number average molecular weight (Mn) of 3946, a weight average molecular weight (Mw) of 8504, and a polydispersity (Mw / Mn) of 2.16.
The GPC chart of the obtained novolak type phenol resin (C-1) is shown in FIG. 3, and the ¹³ C-NMR chart is shown in FIG.

Example 1 Preparation of Esterified Novolac Phenol Resin (Z-1) 20 g of the carboxylic acid-containing novolac phenol resin (C-1) obtained in Production Example 1 and 2- 100 ml of ethoxyethanol was charged, 1 ml of sulfuric acid was added while cooling in an ice bath, and then stirring was continued for 4 hours at room temperature for reaction. After completion of the reaction, sulfuric acid was inactivated with 10 ml of triethylamine, and water was added to the obtained solution to reprecipitate the crude product. The crude product was redissolved in acetone and then reprecipitated with water, then the precipitate was filtered off, vacuum dried, and 21.3 g of a novolak-type esterified phenol resin (Z-1) of a light-colored powder. Got

The obtained esterified novolak-type phenol resin (Z-1) had a number average molecular weight (Mn) of 3183, a weight average molecular weight (Mw) of 5180, and a polydispersity (Mw / Mn) of 1.62. The esterification rate of the obtained esterified novolak-type phenol resin (Z-1) ^{calculated from 13} C-NMR was 52%.
The GPC chart of the esterified novolak type phenol resin (Z-1) is shown in FIG. ^{A 13} C-NMR chart of the esterified novolak type phenol resin (Z-1) is shown in FIG.

The esterification rate was calculated from the ratio of the integral value of the carbonyl carbon derived from the carboxyl group observed at 167 to 175 ppm and the integral value of the carbonyl carbon derived from the ester group observed at 155 to 164 ppm.

Example 2 Synthesis of Esterified Novolac Phenol Formaldehyde (Z-2) The reaction was carried out in the same manner as in Example 1 except that 100 ml of 2-propanol was used instead of 100 ml of 2-ethoxyethanol, and the light-colored powder was prepared. 18.3 g of esterified novolak type phenol resin (Z-2) was obtained.

The obtained novolak-type esterified phenol resin (Z-2) had a number average molecular weight (Mn) of 1772, a weight average molecular weight (Mw) of 2554, and a polydispersity (Mw / Mn) of 1.44. The esterification rate of the obtained esterified novolak-type phenol resin (Z-2) ^{calculated from 13} C-NMR was 35%.
The GPC chart of the esterified novolak type phenol resin (Z-2) is shown in FIG. ^{A 13} C-NMR chart of the esterified novolak type phenol resin (Z-2) is shown in FIG.

Example 3 Synthesis of esterified novolak-type phenol resin (Z-3) The reaction was carried out in the same manner as in Example 1 except that 100 ml of 2-methyl-2-propanol was used instead of 100 ml of 2-ethoxyethanol. 19.2 g of an esterified novolak-type phenol resin (Z-3) of a light-colored powder was obtained.

The obtained esterified novolak-type phenol resin (Z-3) had a number average molecular weight (Mn) of 1074, a weight average molecular weight (Mw) of 1466, and a polydispersity (Mw / Mn) of 1.36. The esterification rate of the obtained esterified novolak-type phenol resin (Z-3) ^{calculated from 13} C-NMR was 15%.
The GPC chart of the esterified novolak type phenol resin (Z-3) is shown in FIG. ^{A 13} C-NMR chart of the esterified novolak type phenol resin (Z-3) is shown in FIG.

Comparative Example 1 Synthesis of Novolac Resin (C'-2) In a 2 L 4-neck flask equipped with a stirrer and a thermometer, 552 g (4 mol) of 2-hydroxybenzoic acid and 498 g of 1,4-bis (methoxymethyl) benzene (498 g) ( 3 mol), 2.5 g of p-toluenesulfonic acid, and 500 g of toluene were charged, heated to 120 ° C., and subjected to a demethanol reaction. The temperature was raised and distilled under reduced pressure, and distillation was carried out under reduced pressure at 230 ° C. for 6 hours to obtain 882 g of a pale yellow solid novolak resin (C'-2).
The number average molecular weight (Mn) of the novolak resin (C'-2) was 1016, the weight average molecular weight (Mw) was 2782, and the polydispersity (Mw / Mn) was 2.74. A GPC chart of the novolak resin (C'-2) is shown in FIG.

Comparative Example 2 Synthesis of Novolac Resin (C'-3) In a 2 L 4-neck flask equipped with a stirrer and a thermometer, m-cresol 648 g (6 mol), p-cresol 432 g (4 mol), and oxalic acid 2.5 g ( 0.028 mol), 492 g of 42% formaldehyde was charged, and the temperature was raised to 100 ° C. for reaction. It was dehydrated and distilled to 200 ° C. at normal pressure, and distilled under reduced pressure at 230 ° C. for 6 hours to obtain 736 g of a pale yellow solid novolak-type phenol resin (C'-3).
The number average molecular weight (Mn) of the novolak resin (C'-3) was 1450, the weight average molecular weight (Mw) was 10316, and the polydispersity (Mw / Mn) was 7.116. A GPC chart of the novolak resin (C'-3) is shown in FIG.

Example 4 Preparation of Photosensitive Composition 20 parts by mass of the esterified novolak-type phenol resin (Z-1) prepared in Example 1 was dissolved in 75 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), and photoacid was dissolved in this solution. 5 parts by mass of the generator was added and dissolved. The obtained solution was microfiltered with a 0.1 μm polytetrafluoroethylene disc filter to prepare a photosensitive composition. The photoacid generator was “TME-triazine” manufactured by Sanwa Chemical Co., Ltd. (2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine) was used.

The following evaluation was performed using the obtained photosensitive composition. The results are shown in Table 1.
(1) Evaluation of Alkaline Developability The obtained photosensitive composition was applied onto a 5-inch silicon wafer with a spin coater to a thickness of about 1 μm, dried on a hot plate at 110 ° C. for 60 seconds, and silicon was used. A resin film was formed on the wafer. This work was repeated, and a plurality of evaluation wafers were prepared.
The evaluation wafer was immersed in an alkaline developer (2.38% aqueous solution of tetramethylammonium hydroxide) for 60 seconds, and after immersion, it was 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 defined as alkali developability (ADR1 (Å / s)).
Two evaluation wafers were prepared, and one of them was designated as an "unexposed sample". ^{The other was used as an "exposed sample" and irradiated with a 200 mJ / cm 2} ghi line using a ghi line lamp ("Multilight" manufactured by Ushio, Inc.), and then heat-treated at 110 ° C. for 120 seconds. .. Both the "unexposed sample" and the "exposed sample" were immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds and then dried on a hot plate at 110 ° C. for 60 seconds. The film thickness of each sample before and after immersion in the developing solution was measured, and the value obtained by dividing the difference by 60 was defined as alkaline developability [ADR2 (Å / s)].
The evaluation wafer was immersed in an alkaline developer (15% aqueous sodium carbonate solution) for 60 seconds, and after immersion, 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 defined as alkali developability (ADR3 (Å / s)).
Two evaluation wafers were prepared, and one of them was designated as an "unexposed sample". ^{The other was used as an "exposed sample" and irradiated with a 200 mJ / cm 2} ghi line using a ghi line lamp ("Multilight" manufactured by Ushio, Inc.), and then heat-treated at 110 ° C. for 120 seconds. .. Both the "unexposed sample" and the "exposed sample" were immersed in an alkaline developer (15% aqueous sodium carbonate solution) for 60 seconds and then dried on a hot plate at 110 ° C. for 60 seconds. The film thickness of each sample before and after immersion in the developing solution was measured, and the value obtained by dividing the difference by 60 was defined as alkaline developability [ADR4 (Å / s)].

(2) Evaluation of Heat Resistance The obtained photosensitive composition was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 μm, and dried on a hot plate at 110 ° C. for 60 seconds. The resin film on the wafer was scraped off, and the glass transition temperature (Tg) thereof was measured and evaluated.
The glass transition temperature (Tg) is measured using a differential scanning calorimeter (DSC) (“Q100” manufactured by TA Instruments Co., Ltd.) in a nitrogen atmosphere, a temperature range of -100 to 200 ° C, and a temperature rise temperature of 10 ° C /. I went on the condition of minutes. When the obtained glass transition temperature was 150 ° C. or higher, it was evaluated as “◯”, and when it was lower than 150 ° C., it was evaluated as “x”.

Example 5-6 and Comparative Example 3-5
A photosensitive composition was prepared and evaluated in the same manner as in Example 4 except that the resin shown in Table 1 was used instead of the esterified novolak type phenol resin (Z-1). The results are shown in Table 1.

As the results in Table 1 show, it can be seen that the photosensitive composition of Comparative Example 3-5 cannot function as a photosensitive composition because alkali elution is observed at the stage before exposure. On the other hand, it can be seen that in the photosensitive composition of Example 4-6, alkali elution was not observed at the stage before exposure, and alkali elution was obtained by exposure, and good development contrast was obtained. It is presumed that this is because the acid of the photoacid generator hydrolyzes the ester group of the esterified novolak type phenol resin of Example 1-3 to form a carboxyl group, thereby changing the polarity.

Claims (8)

A reactant of the formula with an aromatic compound represented by (1) (A) with aliphatic aldehydes (B) a novolac-type phenolic resin and the essential reactant (C) the alcohol compound (X) ,
A reaction product in which some or all of the carboxyl groups in the novolak-type phenol resin (C) derived from the aromatic compound (A) represented by the formula (1) are esterified by the reaction with the alcohol compound (X). A photosensitive composition containing a phenolic hydroxyl group-containing resin and a photoacid generator.

(In the above 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 from 0 to 4.
When R ₁ is a plurality, the plurality of R ₁ may be the same or different.
When R ₂ are a plurality, the plurality of R ₂ may be the same or different.
R ₃ represents a structural site 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.
R ₄ represents a hydroxyl group, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group or a halogen atom.
If R ₄ is plural, R ₄ may be the same or different. ) The photosensitive compound (A) according to claim 1, wherein the aromatic compound (A) is a reaction product of an alkyl-substituted phenol compound and one or more selected from an aromatic aldehyde having a carboxyl group and an aromatic ketone having a carboxyl group. Sex composition. The photosensitive composition according to claim 2, wherein the aromatic aldehyde having a carboxyl group is formylbenzoic acid. The photosensitive composition according to any one of claims 1 to 3, wherein the aliphatic aldehyde (B) is one or more selected from formaldehyde and paraformaldehyde. The photosensitive composition according to any one of claims 1 to 4, wherein the alcohol compound (X) is 1 or more selected from an aliphatic alcohol having 10 or less carbon atoms and an ether alcohol having 10 or less carbon atoms. The photosensitive composition according to any one of claims 1 to 5, wherein the novolak type phenol resin (C) has an esterification rate of the carboxyl group of 5 to 70 mol%. The photosensitive composition according to any one of claims 1 to 6, wherein the phenolic hydroxyl group-containing resin has a number average molecular weight (Mn) in the range of 1,000 to 5,000. A resist film comprising the photosensitive composition according to any one of claims 1 to 7.

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