TWI794578B - Photosensitive composition and resist film - Google Patents

Abstract

The object of the present invention is to provide a resin containing a phenolic hydroxyl group that has high heat resistance and exhibits excellent alkali developability when used as a resist material, and provides a resin containing a phenolic hydroxyl group, which is a novolak type phenol A reaction product of a resin (C) and an alcohol compound (X), wherein the novolak-type phenolic resin (C) contains an aromatic compound (A) and an aliphatic aldehyde (B) represented by the following formula (1) as essential components Reaction raw material.

In formula (1), R ₁ and R ₂ are aliphatic hydrocarbon groups, alkoxy groups, aryl groups, aralkyl groups or halogen atoms having 1 to 9 carbon atoms. m, n and p are integers from 0 to 4.

_R3 is a hydrogen atom, an aliphatic hydrocarbon group with 1 to 9 carbon atoms, or a structural site having one or more substituents selected from alkoxy, halogen and hydroxyl groups on the hydrocarbon group. R ₄ is a hydroxyl group, an aliphatic hydrocarbon group with 1 to 9 carbon atoms, an alkoxy group or a halogen atom.

Description

Photosensitive composition and resist film

The present invention relates to a resin containing a phenolic hydroxyl group, a photosensitive composition, a resist film, a curable composition and a cured product.

In the field of photoresist, various photoresist pattern formation methods that are subdivided according to application and function are being developed one after another. Along with this, the required performance of resin materials for resist is also high and diversified. For example, it is known to use an alkali-soluble resin and 1,2-diazonaphthoquinone (1, 2-naphthoquinonediazide) compound and other photosensitive agent positive photoresist.

As the aforementioned alkali-soluble resin, a positive resist composition using a cresol novolak type epoxy resin has been proposed (for example, refer to Patent Documents 1 and 2).

Positive-type photoresist compositions using cresol novolac-type epoxy resins have been developed for the purpose of improving developability such as sensitivity, but in recent years, patterns tend to become thinner as semiconductors become more integrated. , and require better sensitivity. However, there is a problem that sufficient sensitivity corresponding to line thinning cannot be obtained in a positive resist composition using a cresol novolak type epoxy resin. Furthermore, since various heat treatments are applied in the manufacturing steps of semiconductors and the like, higher heat resistance is also required, but the positive photoresist composition using cresol novolak type epoxy resin has There is a problem of not having sufficient heat resistance.

As the manufacture of a patterned structure using a photoresist, there is a wafer level packaging technology. Wafer-level packaging technology is a packaging technology that performs resin sealing, rewiring, and electrode formation in a wafer state, and singulates by dicing to manufacture semiconductor packages.

In wafer level packaging, as the wiring density increases, the electrochemical deposition method has been used for electronic wiring (for example, refer to Non-Patent Document 1). The reconfigured gold bumps, copper pillars and copper lines for WLP require a resist plated mold. This resist layer is very thick when compared to resist layers used in IC fabrication. The pattern size of the resist mold and the thickness of the resist layer are, for example, 2 μm to 100 μm, which is necessary for patterning with high aspect ratio (resist thickness relative to line size) in photoresist.

For the patterning of high-aspect-ratio photoresists, it has been proposed to use aliphatic polyaldehyde as a cross-linking agent of m-cresol or p-cresol when synthesizing novolac resin (for example, refer to Patent Document 3). However, there is a problem that it is difficult to have both heat resistance and alkali dissolution rate, which are important characteristics of thick film resists.

[Prior Art Literature] [Patent Document]

[Patent Document 1] JP-A-2008-088197

[Patent Document 2] JP-A-2002-107925

[Patent Document 3] Japanese Unexamined Patent Publication No. 9-6003

[Non-patent literature]

[Non-Patent Document 1] Gary Solomon, Electrochemically deposited solder bumps for wafer-level packaging, PACKAGING/ASSEMBLY, Solid State Technology, pages 83,84,86,88 April 2001

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

The inventors of the present invention, as a result of intensive investigations to solve the above-mentioned problems, found that it is a reaction product of a carboxyl group-containing triaryl compound and an aliphatic aldehyde, and a part or all of the carboxyl groups in the aforementioned reaction product are esterified with an alcohol compound. The resultant resin containing phenolic hydroxyl group has excellent heat resistance and alkali developability, and completed the present invention.

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

(前述式(1)中，R₁ 及R₂ 係各自獨立，表示碳原子數1～9之脂肪族烴基、烷氧基、芳基、芳烷基或鹵素原子。 m、n及p係各自獨立，表示0～4之整數。 R₁ 為複數的情形，複數之R₁ 彼此可為相同亦可為相異。 R₂ 為複數的情形，複數之R₂ 彼此可為相同亦可為相異。 R₃ 係表示氫原子、碳原子數1～9之脂肪族烴基、或烴基上具有一個以上選自烷氧基、鹵素基及羥基的取代基的結構部位。 R₄ 係表示羥基、碳原子數1～9之脂肪族烴基、烷氧基或鹵素原子。 R₄ 為複數的情形，複數之R₄ 彼此可為相同亦可為相異。)

(In the above-mentioned formula (1), _R1 and _R2 are each independently, representing an aliphatic hydrocarbon group, an alkoxy group, an aryl group, an aralkyl group or a halogen atom with 1 to 9 carbon atoms. m, n and p are each Independent, representing an integer from 0 to 4. When R ₁ is a plural number, the R _1s of the plural numbers may be the same or different from each other. When R ₂ is a plural number, the R _2s of the plural numbers may be the same or different from each other R ₃ represents a hydrogen atom, an aliphatic hydrocarbon group with 1 to 9 carbon atoms, or a structural site with one or more substituents selected from alkoxy, halogen and hydroxyl groups on the hydrocarbon group. R ₄ represents a hydroxyl group, a carbon atom Aliphatic hydrocarbon groups, alkoxy groups or halogen atoms with numbers 1 to 9. When R ₄ is plural, the plural R ₄ may be the same or different.)

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

[Mode for Carrying Out the Invention]

Hereinafter, one embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and can be implemented by adding appropriate changes within a range not impairing the effects of the present invention.

[Resins containing phenolic hydroxyl groups]

The resin containing phenolic hydroxyl group of the present invention is a reaction product of a novolak-type phenolic resin (C) and an alcohol compound (X), wherein the novolac-type phenolic resin (C) is an aromatic compound represented by the following formula (1): Compound (A) and aliphatic aldehyde (B) are necessary reaction raw materials.

(前述式(1)中，R₁ 及R₂ 係各自獨立，表示碳原子數1～9之脂肪族烴基、烷氧基、芳基、芳烷基或鹵素原子。 m、n及p係各自獨立，表示0～4之整數。 R₁ 為複數的情形，複數之R₁ 彼此可為相同亦可為相異。 R₂ 為複數的情形，複數之R₂ 彼此可為相同亦可為相異。 R₃ 係表示氫原子、碳原子數1～9之脂肪族烴基、或烴基上具有一個以上選自烷氧基、鹵素基及羥基的取代基的結構部位。 R₄ 係表示羥基、碳原子數1～9之脂肪族烴基、烷氧基或鹵素原子。 R₄ 為複數的情形，複數之R₄ 彼此可為相同亦可為相異。)

(In the above-mentioned formula (1), _R1 and _R2 are each independently, representing an aliphatic hydrocarbon group, an alkoxy group, an aryl group, an aralkyl group or a halogen atom with 1 to 9 carbon atoms. m, n and p are each Independent, representing an integer from 0 to 4. When R ₁ is a plural number, the R _1s of the plural numbers may be the same or different from each other. When R ₂ is a plural number, the R _2s of the plural numbers may be the same or different from each other R ₃ represents a hydrogen atom, an aliphatic hydrocarbon group with 1 to 9 carbon atoms, or a structural site with one or more substituents selected from alkoxy, halogen and hydroxyl groups on the hydrocarbon group. R ₄ represents a hydroxyl group, a carbon atom Aliphatic hydrocarbon groups, alkoxy groups or halogen atoms with numbers 1 to 9. When R ₄ is plural, the plural R ₄ may be the same or different.)

The resin containing phenolic hydroxyl group of the present invention has a triarylmethane structure. The triarylmethane structure contains aromatic rings at a high density, so the phenolic hydroxyl group-containing resin of the present invention has very high heat resistance. In the triarylmethane structure of the aforementioned formula (1), the two hydroxyl groups and carboxyl groups are substituted based on their respective different aromatic rings without forming strong hydrogen bonds. Accordingly, the phenolic hydroxyl group-containing resin of the present invention can maintain good proton dissociation properties, and can exhibit excellent alkali developability. In addition, a part or all of the carboxyl groups in the triarylmethane structure is esterified by reaction with the alcohol compound (X), and an extreme polarity change can be induced before and after the hydrolysis of the ester group (before and after carboxyl group formation), and obtain Good development contrast.

[Novolac type phenolic resin] The novolak-type phenolic 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.

(前述式(1)中，R₁ 及R₂ 係各自獨立，表示碳原子數1～9之脂肪族烴基、烷氧基、芳基、芳烷基或鹵素原子。 m、n及p係各自獨立，表示0～4之整數。 R₁ 為複數的情形，複數之R₁ 彼此可為相同亦可為相異。 R₂ 為複數的情形，複數之R₂ 彼此可為相同亦可為相異。 R₃ 係表示氫原子、碳原子數1～9之脂肪族烴基、或烴基上具有一個以上選自烷氧基、鹵素基及羥基的取代基的結構部位。 R₄ 係表示羥基、碳原子數1～9之脂肪族烴基、烷氧基或鹵素原子。 R₄ 為複數的情形，複數之R₄ 彼此可為相同亦可為相異。)

(In the above-mentioned formula (1), _R1 and _R2 are each independently, representing an aliphatic hydrocarbon group, an alkoxy group, an aryl group, an aralkyl group or a halogen atom with 1 to 9 carbon atoms. m, n and p are each Independent, representing an integer from 0 to 4. When R ₁ is a plural number, the R _1s of the plural numbers may be the same or different from each other. When R ₂ is a plural number, the R _2s of the plural numbers may be the same or different from each other R ₃ represents a hydrogen atom, an aliphatic hydrocarbon group with 1 to 9 carbon atoms, or a structural site with one or more substituents selected from alkoxy, halogen and hydroxyl groups on the hydrocarbon group. R ₄ represents a hydroxyl group, a carbon atom Aliphatic hydrocarbon groups, alkoxy groups or halogen atoms with numbers 1 to 9. When R ₄ is plural, the plural R ₄ may be the same or different.)

In the aforementioned formula (1), the aliphatic hydrocarbon groups having 1 to 9 carbon atoms in R ₁ , R ₂ , R ₃ and R ₄ include methyl, ethyl, propyl, isopropyl, and butyl , tertiary butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, etc., alkyl groups with 1 to 9 carbon atoms and cycloalkyl groups with 3 to 9 carbon atoms, etc.

In the aforementioned formula (1), the alkoxy groups of R ₁ , R ₂ and R ₄ include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, cyclo Hexyloxy etc.

In the aforementioned formula (1), the aryl groups of R ₁ and R ₂ include phenyl, tolyl, xylyl, naphthyl, anthracenyl and the like.

In the aforementioned formula (1), the aralkyl groups of _R1 and _R2 include benzyl, phenylethyl, phenylpropyl, naphthylmethyl and the like.

In the aforementioned formula (1), the halogen atoms of R ₁ , R ₂ and R ₄ include fluorine atom, chlorine atom, bromine atom, iodine atom and the like.

In the above-mentioned formula (1), in terms of "the structural site having one or more substituents selected from alkoxy, halogen and hydroxyl groups on the hydrocarbon group" of _R3 , halogenated alkyl, halogenated aryl, 2-methyl Alkoxyalkoxy such as oxyethoxy, 2-ethoxyethoxy, etc., alkylalkoxy substituted with hydroxy, etc.

In the aforementioned formula (1), m and n are each preferably an integer of 2 or 3. In the case where m and n are 2 each, two R ₁ and two R ₂ are each independently an alkyl group having 1 to 3 carbon atoms. In this case, it is preferable that two R ₁ and two R ₂ are each bonded to the 2,5-position of the phenolic hydroxyl group.

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

The aromatic compound (A) represented by said formula (1) may use the same structure individually, and may use plural compounds which have a different molecular structure.

The aromatic compound (A) represented by the aforementioned formula (1) can be prepared, for example, by condensation reaction of an alkyl-substituted phenol (a1) and an aromatic aldehyde (a2) having a carboxyl group. The aromatic compound (A) represented by the aforementioned formula (1) can be prepared, for example, by a condensation reaction of 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 the alkyl group includes an alkyl group having 1 to 8 carbon atoms, preferably a methyl group. Specific examples of the alkyl-substituted phenol (a1) include o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, and p-octylphenol , p-tertiary butylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol and other monoalkylphenols; 2,5-xylenol, 3,5-xylenol, 3,4-di Dialkylphenols such as cresol, 2,4-xylenol, and 2,6-xylenol; trioxanes such as 2,3,5-trimethylphenol and 2,3,6-trimethylphenol base phenol etc. Among them, dialkylphenol is preferable, and 2,5-xylenol and 2,6-xylenol are more preferable. Alkyl-substituted phenols (a1) may be used alone or in combination of two or more.

Aromatic aldehydes (a2) having a carboxyl group include compounds having a formyl group on the benzene ring of benzene, phenol, resorcin, etc., which further have an alkyl, alkoxy, Compounds such as halogen atoms. Specific examples of the aromatic aldehyde (a2) having a carboxyl group include 4-formylbenzoic acid, 2-formylbenzoic acid, 3-formylbenzoic acid, 4-formylbenzoic acid methyl ester, 4-formylbenzoic acid, Ethyl Formylbenzoate, Propyl 4-Formylbenzoate, Isopropyl 4-Formylbenzoate, Butyl 4-Formylbenzoate, Isobutyl 4-Formylbenzoate, 4-Benzene Formylbenzoate Tertiary butyl formate, cyclohexyl 4-formylbenzoate, tertiary octyl 4-formylbenzoate, etc. Among these, 4-formylbenzoic acid is preferred. The aromatic aldehyde (a2) which has a carboxyl group may be used individually by 1 type, and may use 2 or more types together.

The aromatic ketone (a3) having a carboxyl group is a compound having at least one carboxyl group and carbonyl group in an aromatic ring. Specific examples of the aromatic ketone (a3) having a carboxyl group include, for example, 2-acetylbenzoic acid, 3-acetylbenzoic acid, 4-acetylbenzoic acid, and 2-acetylbenzoic acid. Methyl Benzoate, Ethyl 2-Acetylbenzoate, Propyl 2-Acetylbenzoate, Isopropyl 2-Acetylbenzoate, Butyl 2-Acetylbenzoate, 2-Acetylbenzoate Isobutyl benzoate, tertiary butyl 2-acetylbenzoate, cyclohexyl 2-acetylbenzoate, tertiary octyl 2-acetylbenzoate, etc. Among these, 2-acetylbenzoic acid and 4-acetylbenzoic acid are preferable. Aromatic ketones (a3) may be used alone or in combination of two or more.

𠮿(1,3,5-trioxane)、乙醛、丙醛、四聚甲醛(tetraoxymethylene)、聚甲醛(polyoxymethylene)、氯醛(chloral)、六亞甲四胺(hexamethylenetetramine)、乙二醛(glyoxal)、正丁基醛、己醛、烯丙醛、巴豆醛(crotonaldehyde)、丙烯醛(acrolein)等。 脂肪族醛化合物(B)係可單獨使用一種，亦可併用二種以上。Specific examples of the aliphatic aldehyde (B) include formaldehyde, paraformaldehyde, 1,3,5-tri

𠮿(1,3,5-trioxane), acetaldehyde, propionaldehyde, tetraoxymethylene, polyoxymethylene, chloral, hexamethylenetetramine, glyoxal ), n-butylaldehyde, hexanal, allylaldehyde, crotonaldehyde, acrolein, etc. The aliphatic aldehyde compound (B) may be used alone or in combination of two or more.

The aliphatic aldehyde (B) is preferably at least one selected from formaldehyde and paraformaldehyde, more preferably formaldehyde. When using formaldehyde and an aliphatic aldehyde other than formaldehyde as the aliphatic aldehyde (B), the amount of the aliphatic aldehyde other than formaldehyde used is preferably in the range of 0.05 to 1 mole per 1 mole of formaldehyde.

The manufacturing method of a novolak type phenolic resin (C) preferably comprises the following 3 steps 1-3. (step 1) Alkyl-substituted phenol (a1) and carboxyl-containing aromatic aldehyde (a2) are heated in the range of 60-140°C in the presence of an acid catalyst, and a solvent is used if necessary, to obtain aromatic compounds through polycondensation. Group 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 aliphatic aldehyde (B) isolated in step 2 are heated in the range of 60-140°C in the presence of an acid catalyst, using a solvent if necessary, and polycondensed to obtain a novolak Type phenolic resin (C).

As for the acid catalyst used in the above step 1 and step 3, for example, acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, manganese acetate, etc. can be mentioned. These acid catalysts may be used alone or in combination of two or more. Also, among these acid catalysts, sulfuric acid and p-toluenesulfonic 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. In addition, the acid catalyst may be added before the reaction, or may be added during the reaction.

烷、1,4-二

烷等之環狀醚；乙二醇乙酸酯等之二醇酯；丙酮、甲基乙基酮、甲基異丁基酮等之酮；甲苯、二甲苯等之芳香族烴等。此等之溶媒可僅使用一種，亦可併用二種以上。又，此等之溶媒中，由獲得的化合物之溶解性優異的觀點來看，較佳為2-乙氧基乙醇。As for the solvent used as necessary in the above-mentioned step 1 and step 3, for example: methanol, ethanol, propanol and other alcohols; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 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 Glycol ethers of alcohol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether, etc.; 1,3-diol

Alkane, 1,4-bis

Cyclic ethers such as alkanes; glycol esters such as ethylene glycol acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; aromatic hydrocarbons such as toluene and xylene, etc. These solvents may be used alone or in combination of two or more. Also, among these solvents, 2-ethoxyethanol is preferable from the viewpoint of excellent solubility of the obtained compound.

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

The feed ratio [(A)/(B)] of the aromatic compound (A) and the aliphatic aldehyde (B) in step 3 can suppress excessive high molecular weight (gelation) and can be obtained as an inhibitor From the viewpoint of the appropriate molecular weight of the phenol resin, the molar ratio is preferably in the range of 1/0.5 to 1/1.2, more preferably in the range of 1/0.6 to 1/0.9.

烷、1,4-二

烷等之環狀醚；乙二醇乙酸酯等之二醇酯；丙酮、甲基乙基酮、甲基異丁基酮等之酮等。又，於使用水作為前述不良溶媒(S1)的情形，就前述(S2)而言，較佳為丙酮。又，前述不良溶媒(S1)及溶媒(S2)係各自可僅使用一種，亦可併用二種以上。As the method of isolating the aromatic compound (A) from the reaction solution in step 2, for example, the reaction solution is poured into a poor solvent (S1) that is insoluble or poorly soluble in the reaction product and filtered off. After the precipitation, the reaction product is dissolved and dissolved in the solvent (S2) which is also mixed with the poor solvent (S1), and then thrown into the poor solvent (S1) again to filter out the generated precipitate. In terms of the aforementioned poor solvent (S1) used at this time, for example: water; monohydric alcohols such as methanol, ethanol, and propanol; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, and cyclohexane ; Aromatic hydrocarbons such as toluene and xylene. Among these poor solvents (S1), water and methanol are preferable from the viewpoint that the removal of the acid catalyst can be efficiently performed simultaneously. On the other hand, examples of the aforementioned solvent (S2) include monohydric alcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol; Alcohol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene Polyols such as glycol, polyethylene glycol, and glycerin; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl glycol ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether, etc.; 1,3-diol

Alkane, 1,4-bis

Cyclic ethers such as alkanes; glycol esters such as ethylene glycol acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Moreover, when using water as said poor solvent (S1), it is preferable that it is acetone for said (S2). Moreover, each of said poor solvent (S1) and solvent (S2) may use only 1 type, and may use 2 or more types together.

In the case of using aromatic hydrocarbons such as toluene and xylene as the solvent in the above-mentioned step 1 and step 3, if heating is carried out above 80°C, the above-mentioned aromatic compound (A) generated by the reaction is dissolved in the solvent, and directly Upon cooling, crystals of the aromatic compound (A) are precipitated, and thus the aromatic compound (A) can be isolated by filtering it off. In this case, the aforementioned poor solvent (S1) and solvent (S2) may not be used.

The aromatic compound (A) represented by the aforementioned formula (1) can be obtained by the above-mentioned isolation method in step 2. The purity of the aromatic compound (A) is calculated from a gel permeation chromatography (GPC) chart, and is preferably at least 90%, more preferably at least 94%, and most preferably at least 98%. The purity of the aromatic compound (A) can be obtained from the area ratio of the graph of GPC, and is measured under the measurement conditions described later.

The weight average molecular weight (Mw) of a novolac type phenolic resin (C) becomes like this. Preferably it is the range of 2,000-35,000, More preferably, it is the range of 2,000-25,000. The weight average molecular weight (Mw) of a novolak type phenolic resin (C) is measured by the following measurement conditions using gel permeation chromatography (it abbreviates to "GPC" hereafter).

(GPC measurement conditions) 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 Refractometer) Data processing: "GPC-8020 Model II Version 4.30" manufactured by Tosoh Co., Ltd. Eluent: Tetrahydrofuran Flow rate: 1.0mL/min

Sample: A solution obtained by filtering a tetrahydrofuran solution of 0.5% by mass in terms of resin solid content through a microfilter (100 μl)

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.

"F-1" manufactured by Tosoh Co., Ltd.

"F-2" manufactured by Tosoh Co., Ltd.

"F-4" manufactured by Tosoh Co., Ltd.

"F-10" manufactured by Tosoh Co., Ltd.

"F-20" manufactured by Tosoh Co., Ltd.

[Alcohol compound (X)]

The resin containing phenolic hydroxyl group of the present invention is a reaction product of a novolak type phenolic resin (C) and an alcohol compound (X). Here, the reaction of the novolac 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, tertiary butyl alcohol, ethylene glycol, Aliphatic alcohols with less than 10 carbon atoms such as propylene glycol and trimethylolpropane; aromatic alcohols with less than 10 carbon atoms such as benzyl alcohol; 2-methoxyethyl alcohol, 2-ethoxyethyl alcohol Alcohol, 1-methoxy-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, 3-methoxy-1-butyl alcohol, 2-isopropoxyethyl alcohol, etc. Ether alcohols with less than 10 carbon atoms in the ether bond; ketone alcohols with less than 10 carbon atoms including ketone groups such as 3-hydroxy-2-butanone; carbon atoms including ester groups such as methyl hydroxyisobutyrate Ester alcohols whose number is less than 10, etc. Among them, preferred are aliphatic alcohols with 10 or less carbon atoms and ether alcohols with 10 or less carbon atoms, more preferably ethyl alcohol, n-propyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, isobutyl alcohol (2-methyl-2-propanol), tert-butyl alcohol and 2-ethoxyethyl alcohol (2-ethoxyethanol). The said alcohol compound (X) may be used individually by 1 type, and may use 2 or more types together.

The aforementioned dehydration esterification reaction can be carried out by stirring the mixture of the novolac type phenolic 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, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts may be used alone or in combination of two or more. The reaction temperature is not particularly limited, and may be, for example, in the range of 10°C to 60°C, and is preferably room temperature from the viewpoint that no special equipment is required.

The dehydration esterification reaction between the novolak-type phenol resin (C) and the alcohol compound (X) is derived from the carboxyl group and alcohol in the novolac-type phenol resin (C) of the aromatic compound (A) represented by the aforementioned formula (1). Compound (X) reacts to form an ester bond accompanied by dehydration. The feed ratio of the novolak-type phenolic resin (C) to the alcohol compound (X) in the aforementioned dehydration esterification reaction is not particularly limited, and is, for example, phenol resin/alcohol = 1/0.5 to 1/10 in terms of weight ratio.

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

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

[Photosensitive composition] The photosensitive composition of the present invention includes the phenolic hydroxyl-containing resin and the photoacid generator of the present invention. The aforementioned photoacid generator is not particularly limited, and known photoacid generators can be used, for example, organic halogen compounds, sulfonate esters, onium salts, diazonium salts, dioxane compounds, and the like.

、參(三溴甲基)-s-三

、參(二溴甲基)-s-三

、2,4-雙(三溴甲基)-6-對甲氧基苯基-s-三

、(2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三

)等之含有鹵烷基的s-三

衍生物；The following are mentioned about the specific example of the said photo-acid generator. ginseng(trichloromethyl)-s-tri

, ginseng (tribromomethyl)-s-three

, ginseng (dibromomethyl)-s-three

, 2,4-bis(tribromomethyl)-6-p-methoxyphenyl-s-tri

, (2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-tri

) etc. containing haloalkyl s-three

derivative;

Halogen-substituted paraffinic hydrocarbon compounds such as 1,2,3,4-tetrabromobutane, 1,1,2,2-tetrabromoethane, carbon tetrabromide, iodoform, etc.; hexabromocyclohexane, hexachloro Halogen-substituted cycloparaffinic hydrocarbon compounds such as cyclohexane and hexabromocyclododecane;

Haloalkyl-containing benzene derivatives of bis(trichloromethyl)benzene, bis(tribromomethyl)benzene, etc.; Halogen compounds; 2,3-dibromocyclobutane and other halogen-containing cyclobutane compounds; ginseng (2,3-dibromopropyl) isocyanate and other haloalkyl-containing isocyanate compounds;

Triphenylcoldium chloride, diphenyl-4-methylphenylcolumbite trifluoromethanesulfonate, triphenylcolumbite methanesulfonate, triphenylcolumbite trifluoromethanesulfonate, triphenylcolumbite para Toluene sulfonate, triphenylconerium tetrafluoroborate, triphenylconerium hexafluoroarsenate, triphenylconerium hexafluorophosphate, etc.;

Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphate, etc. salt;

Methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, phenyl p-toluenesulfonate, 1,2,3-ginseng (p-toluenesulfonyloxy)benzene, benzene p-toluenesulfonate Azoin ester, methyl methanesulfonate, ethyl methanesulfonate, butyl methanesulfonate, 1,2,3-paraffin(methanesulfonyloxy)benzene, phenyl methanesulfonate, benzoin methanesulfonate ester, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, butyl trifluoromethanesulfonate, 1,2,3-paraffin (trifluoromethanesulfonyloxy)benzene, benzene trifluoromethanesulfonate Sulfonate compounds such as esters and benzoin trifluoromethanesulfonate; diphenyl compounds such as diphenyldisulfonate;

Bis(phenylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, cyclohexylsulfonyl-( 2-Methoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(3-methoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(4-methoxybenzene Sulfonyl)diazomethane, cyclopentylsulfonyl-(2-methoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(3-methoxyphenylsulfonyl) )diazomethane, cyclopentylsulfonyl-(4-methoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2-fluorophenylsulfonyl)diazomethane, cyclohexyl Sulfonyl-(3-fluorophenylsulfonyl)diazomethane, cyclohexylsulfonyl-(4-fluorophenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2-fluorobenzene Sulfonyl)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) heavy Nitrogen, cyclopentylsulfonyl-(4-chlorophenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2-trifluoromethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl Acyl-(3-trifluoromethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(4-trifluoromethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl- (2-trifluoromethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(3-trifluoromethylphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(4 -Trifluoromethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2-trifluoromethoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(3-trifluoro Methoxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(4-trifluoromethoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(2-trifluoromethane Oxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(3-trifluoromethoxyphenylsulfonyl)diazomethane, cyclopentylsulfonyl-(4-trifluoromethane Oxyphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane, cyclohexylsulfonyl-(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, cyclopentyl Sulfonyl-(2,3,4-triethylphenylsulfonyl)diazomethane, phenylsulfonyl-(2-methoxyphenylsulfonyl) Acyl)diazomethane, phenylsulfonyl-(3-methoxyphenylsulfonyl)diazomethane, phenylsulfonyl-(4-methoxyphenylsulfonyl)diazomethane , bis(2-methoxyphenylsulfonyl)diazomethane, bis(3-methoxyphenylsulfonyl)diazomethane, bis(4-methoxyphenylsulfonyl)diazomethane Methane, phenylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane, phenylsulfonyl-(2,3,4-trimethylphenylsulfonyl) Diazomethane, phenylsulfonyl-(2,4,6-triethylphenylsulfonyl)diazomethane, phenylsulfonyl-(2,3,4-triethylphenylsulfonyl) base) diazomethane, 2,4-dimethylphenylsulfonyl-(2,4,6-trimethylphenylsulfonyl)diazomethane, 2,4-dimethylphenylsulfonyl Base-(2,3,4-trimethylphenylsulfonyl)diazomethane, phenylsulfonyl-(2-fluorophenylsulfonyl)diazomethane, phenylsulfonyl-(3 Diazide compounds of -fluorophenylsulfonyl)diazomethane, phenylsulfonyl-(4-fluorophenylsulfonyl)diazomethane, etc.;

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

N,N'-bis(phenylsulfonyl)hydrazine and other hydrazine compounds;

The percited salts of triarylcaldium, triarylalkylcaldium cations, etc., and salts of sulfonates such as haloalkanesulfonate, arenesulfonate, alkanesulfonate, etc.;

Ionium salts of iodonium cations such as diaryliodonium, and sulfonates of haloalkane sulfonates, arene sulfonates, alkane sulfonates, etc.;

Bis(alkylsulfonyl)diazomethane, bis(cycloalkylsulfonyl)diazomethane, bis(perfluoroalkylsulfonyl)diazomethane, bis(arylsulfonyl)diazomethane , Bis(aralkylsulfonyl)diazomethane and other bissulfonyldiazomethane compounds;

N-sulfonyloxyimine (N- sulfonyloxyimide) compounds;

Benzoin sulfonate compounds such as benzoin tosylate, benzoin mesylate, benzoin butane sulfonate, etc.;

Polyhydroxyarene sulfonate compounds in which all of the hydroxyl groups of polyhydroxyarene sulfonates are replaced by sulfonates of halothane sulfonate, arene sulfonate, alkane sulfonate, etc.;

Nitrobenzyl sulfonate compounds such as (poly)nitrobenzyl fluoroalkane sulfonate, (poly)nitrobenzyl aryl hydrocarbon sulfonate, and (poly)nitrobenzyl alkanesulfonate; (poly)fluoroalkyl benzyl haloalkane sulfonate, (poly)fluoroalkyl benzyl haloalkane sulfonate, (poly)fluoroalkyl benzyl alkanesulfonate, etc.

Bis(arylsulfonyl)alkane compounds;

Bis-O-(arylsulfonyl)-α-dialkylglyoxime, bis-O-(arylsulfonyl)-α-dicycloalkylglyoxime, bis-O-(aryl Sulfonyl)-α-diarylglyoxime, bis-O-(alkylsulfonyl)-α-dialkylglyoxime, bis-O-(alkylsulfonyl)-α-di Cycloalkylglyoxime, bis-O-(alkylsulfonyl)-α-diarylglyoxime, bis-O-(fluoroalkylsulfonyl)-α-dialkylglyoxime, Bis-O-(fluoroalkylsulfonyl)-α-bicycloalkylglyoxime, bis-O-(fluoroalkylsulfonyl)-α-diarylglyoxime, bis-O-( Arylsulfonyl)-α-dialkyldioxime, bis-O-(arylsulfonyl)-α-bicycloalkyldioxime, bis-O-(arylsulfonyl)-α- Diaryldioxime, bis-O-(alkylsulfonyl)-α-dialkyldioxime, bis-O-(alkylsulfonyl)-α-dicycloalkyldioxime, bis-O -(Alkylsulfonyl)-α-diaryldioxime, bis-O-(fluoroalkylsulfonyl)-α-dialkyldioxime, bis-O-(fluoroalkylsulfonyl) - oxime compounds such as α-bicycloalkyldioxime, bis-O-(fluoroalkylsulfonyl)-α-diaryldioxime, etc.;

Arylsulfonyloxyiminoarylacetonitrile, Alkylsulfonyloxyiminoarylacetonitrile, Fluoroalkylsulfonyloxyiminoarylacetonitrile, ((arylsulfonyl)oxy Imino-thiophene-ylidene)arylacetonitrile, (((alkylsulfonyl)oxyimino-thiophene-ylidene)arylacetonitrile, ((fluoroalkylsulfonyl)oxyimino -thiophene-ylidene)arylacetonitrile, bis(arylsulfonyloxyimino)aryldiacetonitrile, bis(alkylsulfonyloxyimino)aryldiacetonitrile, bis(fluoroalkane Sulfonyloxyimino) aryldiacetonitrile, arylfluoroalkanone-O-(alkylsulfonyl)oxime, arylfluoroalkanone-O-(arylsulfonyl)oxime, arylfluoroalkanone-O-(arylsulfonyl)oxime, Modified oxime compounds such as fluoroalkone-O-(fluoroalkylsulfonyl)oxime.

The said photoacid generator may be used individually by 1 type, and may use 2 or more types together. 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, preferably 0.1 parts by mass, with respect to 100 parts by mass of resin solid content in the photosensitive composition. ~10 parts by mass. The photosensitive composition of this invention can be made into the photosensitive composition with high photosensitivity by content of the said photoacid generator being in the said range.

The photosensitive composition of the present invention may contain the phenolic hydroxyl group-containing resin of the present invention and the aforementioned photoacid generator, and may optionally contain other components. Examples of the aforementioned other components include organic base compounds, resins other than the phenolic hydroxyl group-containing resin of the present invention, photosensitizers, surfactants, dyes, fillers, crosslinking 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 aforementioned photoacid generator upon exposure. When the photosensitive composition of the present invention contains the aforementioned organic base compound, the effect of preventing the dimensional variation of the photoresist pattern due to the movement of the acid generated by the aforementioned photoacid generator is obtained.

Specific examples of the aforementioned organic base compound include: pyrimidine, (poly)aminopyrimidine, (poly)hydroxypyrimidine, (poly)amino(poly)hydroxypyrimidine, (poly)amino(poly)alkyl Pyrimidine compounds such as pyrimidines, (poly)amino(poly)alkoxypyrimidines, (poly)hydroxy(poly)alkylpyrimidines, (poly)hydroxy(poly)alkoxypyrimidines, etc.; pyridines, (poly)alkylpyridines Pyridine compounds such as dialkylaminopyridines; polyalkanolamines, tris(hydroxyalkyl)aminoalkanes, bis(hydroxyalkyl)iminoparaffins (hydroxyalkyl)alkanes, etc. containing hydroxyalkyl groups Amine compounds; aminoaryl compounds such as aminophenols, etc. The aforementioned organic base compounds 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 0.1-100 mol%, more preferably in the range of 1-50 mol%, relative to 1 mol of the aforementioned photoacid generator .

The photosensitive composition of the present invention may contain other resins other than the phenolic hydroxyl group-containing resin of the present invention. The aforementioned other resins are not particularly limited, and are, for example, resins soluble in alkaline developing solutions, or resins soluble in alkaline developing solutions by using in combination with additives such as photoacid generators.

The other resins mentioned above include: phenolic resins other than the phenolic hydroxyl group-containing resins of the present invention; p-hydroxystyrene, p-(1,1,1,3,3,3-hexafluoro-2-hydroxypropyl base) homopolymer or copolymer of styrene compounds containing hydroxyl groups such as styrene; Resins modified by acid-decomposable groups; homopolymers or copolymers of (meth)acrylic acid; alicyclic polymerizability of norbornene compounds, tetracyclododecene compounds, etc. Interaction polymers of monomers and maleic anhydride or maleimide, etc.

改質酚樹脂(以三聚氰胺、苯胍

(benzoguanamine)等連結酚核的多價酚化合物)或含有烷氧基的芳香環改質酚醛清漆樹脂(以甲醛連結酚核及含有烷氧基的芳香環的多價酚化合物)等之酚樹脂。Specific examples of phenolic resins other than the phenolic hydroxyl group-containing resins of the present invention include: phenol novolac resins, cresol novolac resins, naphthol novolak resins, co-condensation resins using various phenolic compounds, etc. Novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadienyl phenol addition type resin, phenol aralkyl resin (ZYLOCK resin), naphthol aralkyl resin, trimethylolmethane resin, tetrahydroxy Phenylethane resin (tetraphenylolethane resin), biphenyl modified phenol resin (polyvalent phenol compound with double methylene linking phenol core), biphenyl modified naphthol resin (double methylene linking phenol core polyvalent naphthol compounds), amino three

Modified phenolic resin (based on melamine, benzoguanidine

(Benzoguanamine) and other polyvalent phenolic compounds linked to phenol cores) or alkoxy-containing aromatic ring-modified novolak resins (polyvalent phenolic compounds linked to phenolic cores and alkoxy-containing aromatic rings with formaldehyde) and other phenolic resins .

Among the specific examples of the phenolic resin other than the phenolic hydroxyl group-containing resin of the present invention, cresol novolac is preferred from the viewpoint of forming a photosensitive composition with excellent balance between developability, heat resistance, and fluidity. Resins, and cresol and other phenolic compounds of the co-condensed novolac resin. Cresol novolak resin or cresol and other phenolic compound co-descapsulated novolak resin, specifically, one or more cresols and aldehyde compounds selected from o-cresol, m-cresol and p-cresol as The necessary reaction raw materials, and the novolac resin obtained by using other appropriate phenolic compounds.

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

The photosensitive composition of the present invention may contain photosensitizers commonly used in resist materials. The aforementioned photosensitizer is, for example, a compound having a quinonediazide group. Specific examples of the compound having a quinonediazide group include ester compounds or amides of an aromatic (poly)hydroxy compound and a sulfonic acid compound having a quinonediazide group. In addition, the above-mentioned ester compound also includes the meaning of a partial ester compound, and the aforementioned amidate includes the meaning of a partial amidate.

Specific examples of the aforementioned sulfonic acid compound having a quinonediazide group include naphthoquinone-1,2-diazido-5-sulfonic acid, naphthoquinone-1,2-diazido-4 -sulfonic acid, o-anthraquinonediazidosulfonic acid, 1,2-naphthoquinone-2-diazido-5-sulfonic acid, etc. As specific examples of the aforementioned sulfonic acid compound having a quinonediazide group, a halide further substituted with a halogen can also be used.

Examples of the aforementioned aromatic (poly)hydroxyl compounds include: 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, Hydroxydiphenylketone, 2,3,6-trihydroxydiphenylketone, 2,3,4-trihydroxy-2'-methyldiphenylketone, 2,3,4,4'-tetrahydroxydiphenylketone Phenyl ketone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4',6-pentahydroxybenzophenone, 2,2',3,4,4 '-pentahydroxybenzophenone, 2,2',3,4,5-pentahydroxybenzophenone, 2,3',4,4',5',6-hexahydroxybenzophenone, 2 , Polyhydroxybenzophenone compounds such as 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]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 substitutions; Bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4 -Hydroxyphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy- 2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2- hydroxyphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3 -Methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-2-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-substituent, etc.

The said photosensitizer may be used individually by 1 type, and may use 2 or more types together. The content of the photosensitive agent in the photosensitive composition of the present invention is preferably from the viewpoint of forming a photosensitive composition excellent in photosensitivity relative to the total of 100 parts by mass of the resin components of the photosensitive composition of the present invention. It is 5-50 mass parts.

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

The said surfactant may be used individually by 1 type, and may use 2 or more types together. It is preferable that content of the said surfactant in the photosensitive composition of this invention is 0.001-2 mass parts with respect to the total 100 mass parts of resin components of the photosensitive composition of this invention.

烷等之環式醚；2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、氧乙酸乙酯(ethyl oxyacetate)、2-羥基-3-甲基丁酸甲酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、甲酸乙酯、乙酸乙酯、乙酸丁酯、乙醯乙酸甲酯、乙醯乙酸乙酯等之酯化合物。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. As for the aforementioned organic solvent, for example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, etc. Alkylene Glycol Monoalkyl Ether; Diethylene Glycol Dimethyl Ether, Diethylene Glycol Diethyl Ether, Diethylene Glycol Dipropyl Ether, Diethylene Glycol Dibutyl Ether, etc. Dialkyl glycol dialkyl ether; alkylene glycol alkyl ether acetate such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc. Esters; ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone, etc.; two

Cyclic ethers of alkanes, etc.; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate ), 2-hydroxy-3-methylbutyrate methyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, Esters of butyl acetate, methyl acetylacetate, ethyl acetylacetate, etc.

The aforementioned organic solvents may be used alone or in combination of two or more. The content of the said organic solvent in the photosensitive composition of this invention is not specifically limited, For example, it can be set as the amount which can fully dissolve the phenolic hydroxyl group containing resin of this invention in a photosensitive composition.

The photosensitive composition of the present invention can be produced by blending the above-mentioned components and mixing them using a mixer or the like. Also, when the photosensitive composition of the present invention contains a filler or a pigment, it can be produced by dispersing or mixing using a dispersing device 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. In the case of using the photosensitive composition of the present invention as a resist material, the photosensitive composition of the present invention can be used directly as a coating material, or the photosensitive composition of the present invention can be coated on a support film, and the The obtained coating film was subjected to desolventization to serve as a resist film. Examples of the support film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. The aforementioned supporting film may be a single-layer film or a laminated film composed of multiple films. In addition, the surface of the aforementioned support film may be corona-treated or coated with a release agent.

As a method of general photolithography using the photosensitive composition of the present invention, for example, the following methods are mentioned. Firstly, the photosensitive composition of the present invention is coated on a silicon substrate, a silicon carbide substrate, a gallium nitride substrate, etc., to be subjected to photolithography, and prebaked at a temperature of 60-150°C. The coating method at this time may be any method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor blade coating or the like. Then, the photoresist pattern is formed by exposing through the photoresist pattern and developing with an alkali developing solution.

When using the photosensitive composition of this invention for resist permanent film use, you may contain a crosslinking agent. Examples of the crosslinking agent include the same ones as the curing agents contained in the curable composition described later. The aforementioned crosslinking agents may be used alone or in combination of two or more.

As a method of forming the resist permanent film, for example, the following methods are mentioned. Firstly, the photosensitive composition of the present invention is coated on a silicon substrate, a silicon carbide substrate, a gallium nitride substrate, etc. to be subjected to photolithography, and pre-baked at a temperature of 60-150°C. The coating method is the same as the previous example. Next, it is exposed through the photoresist pattern, and after thermal curing under the temperature condition of 110-210° C., the photoresist pattern is formed by developing with an alkali developing solution. Alternatively, after exposure, it may be developed with an alkaline developer, and then thermally cured at a temperature of 110-210°C.

Specific examples of resist permanent films include solder resists, packaging materials, underfill materials, packaging adhesive layers for circuit components, integrated circuit components, and circuit substrates in semiconductor devices. The next layer and so on. Moreover, in thin displays represented by LCD and OELD, a thin film transistor protective film, a liquid crystal color filter protective film, a black matrix, a spacer, etc. are mentioned.

唑啉化合物等。[Curable composition] The curable composition of the present invention comprises the phenolic hydroxyl-containing resin of the present invention and a hardener. The aforementioned curing agent is not particularly limited as long as it can react with the phenolic hydroxyl-containing resin of the present invention, and is not particularly limited. For example, melamine compounds, guanamine compounds, acetylene urea compounds, Urea compounds, resols, epoxy compounds, isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, acid anhydrides,

Azoline compounds, etc.

The aforementioned melamine compounds include, for example, hexamethylolmelamine, hexamethoxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylolmelamine are methoxymethylated, hexamethoxymethylmelamine, and hexamethoxymethylmelamine. Ethyl melamine, hexayloxymethyl melamine, compounds in which 1 to 6 methylol groups of hexamethylol melamine have been methylated with acyloxy groups, etc.

、四羥甲基胍胺之1～4個羥甲基經甲氧基甲基化的化合物、四甲氧基乙基胍胺、四醯氧基胍胺、四羥甲基胍胺之1～4個羥甲基經醯氧基甲基化的化合物等。As the aforementioned guanamine compounds, for example, tetrahydroxymethylguanamine, tetramethoxymethylguanamine, tetramethoxymethylbenzoguanamine,

, 1 to 4 methylol groups of tetrahydroxymethylguanamine are methoxymethylated compounds, tetramethoxyethylguanamine, tetraacyloxyguanamine, 1 to 4 methylolguanamines Compounds in which 4 hydroxymethyl groups are methylated with acyloxy groups, etc.

As the aforementioned acetylene carbamide compound, for example, 1,3,4,6-tetra(methoxymethyl)acetylene carbamide, 1,3,4,6-tetra(butoxymethyl)acetylene carbamide, 1,3,4,6-Tetra(hydroxymethyl)acetylene carbamide, etc.

As the aforementioned urea compound, for example, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetra(butoxymethyl)urea and 1,1,3,3-tetra (Methoxymethyl)urea, etc.

As the above-mentioned resol resin, for example, bisphenols such as alkylphenols such as phenol, cresol or xylenol, phenylphenol, resorcinol, biphenyl, bisphenol A or bisphenol F, etc. A polymer obtained by reacting compounds containing phenolic hydroxyl groups such as phenol, naphthol, and dihydroxynaphthalene with aldehyde compounds under alkaline catalyst conditions.

As the aforementioned epoxy compound, for example, diglycidyloxynaphthalene, phenol novolak type epoxy resin, cresol novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol Novolac-type epoxy resin, naphthol-cresol novolak-type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, 1,1-bis(2, 7-diglycidyloxy-1-naphthyl)alkane, naphthyl ether type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phosphorus-containing Atomic epoxy resins, polyglycidyl ethers of co-condensates of compounds containing phenolic hydroxyl groups and aromatic compounds containing alkoxy groups, etc.

As said isocyanate compound, for example, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate etc. are mentioned.

As the aforementioned azide compound, for example, 1,1'-biphenyl-4,4'-bisazide, 4,4'-methinebisazide, 4,4'- Oxybis azide (4,4'-oxybis azide) and so on.

As the compound containing a double bond such as an alkenyl ether group, for example, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propylene glycol divinyl ether, 1,4 -Butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1, 4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, neopentylthritol trivinyl ether, neopentylthritol tetravinyl ether, sorbitol tetravinyl ether, Sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, etc.

The aforementioned acid anhydrides include, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, Aromatic anhydrides such as carboxylic dianhydride, 4,4'-(isopropylidene)diphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, etc.; Tetrahydro Phthalic Anhydride, Methyltetrahydrophthalic Anhydride, Hexahydrophthalic Anhydride, Methylhexahydrophthalic Anhydride, Endomethylenetetrahydrophthalic Anhydride Dodecenylsuccinate Acid anhydrides, alicyclic carboxylic anhydrides such as trialkyltetrahydrophthalic anhydrides, etc.

Among the above curing agents, acetylene carbamide compounds, urea compounds, and resol resins are preferred, and acetylene carbamide compounds are more preferred from the viewpoint of obtaining a cured product having high curability and excellent heat resistance.

The aforementioned curing agents 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 relative to 100 parts by mass of the total 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. The aforementioned other components include resins other than the phenolic hydroxyl group-containing resin of the present invention, curing accelerators, surfactants, dyes, fillers, crosslinking agents, dissolution accelerators, and the like.

改質酚樹脂、乙烯基聚合物等。The curable composition of the present invention may contain other resins than the phenolic hydroxyl group-containing resin of the present invention. Examples of the aforementioned other resins include 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 novolac resin, phenol aralkyl resin (ZYLOCK resin), naphthol aralkyl resin, trimethylol methane resin, tetrahydroxyphenyl ethane resin, biphenyl modified phenol resin, biphenyl modified phenol resin, Phenyl modified naphthol resin, amino three

Modified phenolic resin, vinyl polymer, etc.

Specific examples of the above-mentioned novolak resins include alkylphenols such as phenol, cresol, and xylenol, phenylphenol, resorcinol, biphenyl, bisphenol A, or bisphenol F. Compounds containing phenolic hydroxyl groups such as bisphenols, naphthols, and dihydroxynaphthalene, and polymers obtained by reacting with aldehyde compounds under acid catalyst conditions, etc.

Specific examples of the aforementioned vinyl polymers include polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, poly Vinyl compounds such as norbornene, polycyclodecene, polytetracyclododecene, polytricyclo[2.2.1.0(2,6)]heptane (poly nortricyclene), poly(meth)acrylate, etc. Homopolymers, or copolymers of these, etc.

The aforementioned other resins may be used alone or in combination of two or more. The content of the aforementioned other resins in the curable composition of the present invention is not particularly limited, and can be set arbitrarily according to the intended use. For example, 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 other resin is preferably 0.5 to 100 parts by mass.

The curable composition of the present invention may contain a curing accelerator. Specific examples of the aforementioned hardening accelerator include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, manganese acetate, and the aforementioned photoacid generators.

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

烷等之環式醚；2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、氧乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、甲酸乙酯、乙酸乙酯、乙酸丁酯、乙醯乙酸甲酯、乙醯乙酸乙酯等之酯化合物。The curable composition of the present invention is preferably in a state where the phenolic hydroxyl group-containing resin of the present invention is dissolved in an organic solvent. As for the aforementioned organic solvent, for example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, etc. Alkylene Glycol Monoalkyl Ether; Diethylene Glycol Dimethyl Ether, Diethylene Glycol Diethyl Ether, Diethylene Glycol Dipropyl Ether, Diethylene Glycol Dibutyl Ether, etc. Dialkyl glycol dialkyl ether; alkylene glycol alkyl ether acetate such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc. Esters; ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone, etc.; two

Cyclic ethers of alkanes, etc.; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2- Methyl hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, Ester compounds such as methyl acetoacetate and ethyl acetoacetate.

The aforementioned organic solvents may be used alone or in combination of two or more. The content of the aforementioned organic solvent in the curable composition of the present invention is not particularly limited, for example, may be set to an amount that can completely dissolve 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 the above-mentioned components and mixing them using a mixer or the like. Also, when the curable composition of the present invention contains a filler or a pigment, it can be produced by dispersing or mixing using a dispersing device such as a dissolver, a homogenizer, and a three-roller 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. In the case of using the curable composition of the present invention as a resist material, the curable composition of the present invention can be used directly as a coating material, or the curable composition of the present invention can be coated on a support film, and the The obtained coating film was desolventized and used as a resist film. Examples of the support film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. The aforementioned supporting film may be a single-layer film or a laminated film composed of multiple films. In addition, the surface of the aforementioned 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 methods for forming a resist underlayer film include the following. Apply the curable composition of the present invention on a silicon substrate, a silicon carbide substrate, a gallium nitride substrate, etc. to be subjected to photolithography, and dry it at a temperature of 100 to 200°C, and then dry it at a temperature of 250 to Under the temperature condition of 400°C, it is heated and hardened to form a resist underlayer film. Next, a photoresist pattern is formed on the underlayer film by a usual photoetching method, and a photoresist pattern by a multilayer resist method is formed 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 appropriate methods such as thermal curing and photo curing according to the type of curing agent, the type of curing accelerator, and the like. The curing conditions such as the heating temperature and time in thermal curing, the type of light or exposure time in photocuring can be appropriately adjusted according to the type of curing agent, the type of curing accelerator, and the like. [Example]

Hereinafter, the present invention will be specifically described based on examples and comparative examples. Moreover, the number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity (Mw/Mn) of the resin prepared in the Example were measured by the following GPC measurement conditions. [Measurement conditions of GPC] Measuring device: "HLC-8220 GPC" manufactured by Tosoh Co., Ltd. String: "Shodex KF802" (8.0mmФ×300mm) made by Showa Denko Co., Ltd. + "Shodex KF802" made by Showa Denko Co., Ltd. (8.0mmФ×300mm) + "Shodex KF803" made 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 Refractometer) Data processing: "GPC-8020 Model II Version 4.30" manufactured by Tosoh Co., Ltd. Eluent: Tetrahydrofuran Flow rate: 1.0mL/min Sample: obtained by filtering a tetrahydrofuran solution of 0.5% by mass in terms of resin solid content through 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. "F-1" manufactured by Tosoh Co., Ltd. "F-2" manufactured by Tosoh Co., Ltd. "F-4" manufactured by Tosoh Co., Ltd. "F-10" manufactured by Tosoh Co., Ltd. "F-20" manufactured by Tosoh Co., Ltd.

In the measurement of the ¹³ C-NMR spectrum in the examples, "AL-400" manufactured by JEOL Co., Ltd. was used to analyze the DMSO-d ₆ solution of the sample for structural analysis. The measurement conditions for 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: 30wt% Cumulative times: 10000 times

Synthesis example 1 Synthesis of phenolic trinuclear compound containing carboxylic acid 293.2 g (2.4 mol) of 2,5-xylenol and 150 g (1 mol) of 4-formylbenzoic acid were fed into a 2000 ml 4-necked flask equipped with a cooling tube, and dissolved in 500 ml of acetic acid. After adding 5 ml of sulfuric acid while cooling in an ice bath, it was heated at 100° C. for 2 hours with a heating mantle, and stirred to react. After the reaction, the obtained solution was reprecipitated with water to obtain a crude product. The crude product was redissolved in acetone, and further reprecipitated with water, and the obtained product was filtered off and vacuum-dried to obtain 283 g of a precursor compound (A-1) in pale pink crystals.

As a result of ¹³ C-NMR spectrum measurement, the obtained precursor compound (A-1) was confirmed to be a compound represented by the following structural formula. Also, 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. 2 .

Production Example 1 Synthesis of Novolak-type Phenolic Resin Containing Carboxylic Acid After feeding 188 g of precursor compound (A-1) and 16 g of 92% paraformaldehyde (B-1) into a 1000 ml 4-neck flask equipped with a cooling tube, Dissolve in 500ml of acetic acid. After adding 10 ml of sulfuric acid while cooling in an ice bath, it was heated to 80° C. in an oil bath, and reacted while 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, further reprecipitated with water, and the precipitate was filtered off and vacuum-dried to obtain 182 g of novolak-type phenol resin (C-1) as an orange powder. The number average molecular weight (Mn) of the obtained novolac type phenol resin (C-1) was 3946, the weight average molecular weight (Mw) was 8504, and the polydispersity (Mw/Mn) was 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. 4 .

Embodiment 1 The preparation of esterified novolac type phenolic resin (Z-1) Feed 20 g of the carboxylic acid-containing novolak type phenol resin (C-1) obtained in Production Example 1 and 100 ml of 2-ethoxyethanol into a 300 ml 4-neck flask equipped with a cooling tube, and cool in an ice bath. After adding 1 ml of sulfuric acid, stirring was continued at room temperature for 4 hours to allow reaction. After completion of the reaction, sulfuric acid was deactivated with 10 ml of triethylamine, water was added to the obtained solution, and the crude product was reprecipitated. The crude product was redissolved in acetone, further reprecipitated with water, and the precipitate was filtered off and vacuum-dried to obtain 21.3 g of novolak-type esterified phenol resin (Z-1) as light orange powder.

The number average molecular weight (Mn) of the obtained esterified novolak type phenolic resin (Z-1) was 3183, the weight average molecular weight (Mw) was 5180, and the polydispersity (Mw/Mn) was 1.62. In addition, the esterification rate calculated from ¹³ C-NMR of the obtained esterified novolak-type phenol resin (Z-1) was 52%. The GPC chart of the esterified novolac type phenol resin (Z-1) is shown in FIG. 5 . The ¹³ C-NMR chart of the esterified novolak-type phenol resin (Z-1) is shown in FIG. 6 .

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

Example 2 Synthesis of Esterified Novolak Type Phenolic Resin (Z-2) Except having used 100 ml of 2-propanol instead of 100 ml of 2-ethoxyethanol, it reacted similarly to Example 1, and obtained 18.3 g of esterified novolac type phenol resins (Z-2) of light orange powder.

The number average molecular weight (Mn) of the obtained novolac type esterified phenol resin (Z-2) was 1772, the weight average molecular weight (Mw) was 2554, and the polydispersity (Mw/Mn) was 1.44. In addition, the esterification rate calculated from ¹³ C-NMR of the obtained esterified novolak-type phenol resin (Z-2) was 35%. The GPC chart of the esterified novolac type phenol resin (Z-2) is shown in FIG. 7 . The ¹³ C-NMR chart of the esterified novolak-type phenol resin (Z-2) is shown in FIG. 8 .

Example 3 Synthesis of Esterified Novolak Type Phenolic Resin (Z-3) Except that 100 ml of 2-methyl-2-propanol was used instead of 100 ml of 2-ethoxyethanol, the reaction was carried out in the same manner as in Example 1 to obtain an esterified novolak-type phenol resin (Z-3) of light orange powder 19.2 g.

The number average molecular weight (Mn) of the obtained esterified novolak type phenolic resin (Z-3) was 1074, the weight average molecular weight (Mw) was 1466, and the polydispersity (Mw/Mn) was 1.36. In addition, the esterification rate calculated from ¹³ C-NMR of the obtained esterified novolak-type phenol resin (Z-3) was 15%. The GPC chart of the esterified novolac type phenol resin (Z-3) is shown in FIG. 9 . The ¹³ C-NMR chart of the esterified novolac type phenol resin (Z-3) is shown in FIG. 10 .

Comparative Example 1 Synthesis of Novolak Resin (C'-2) 552g (4mol) of 2-hydroxybenzoic acid, 498g (3mol) of 1,4-bis(methoxymethyl)benzene, 2.5g of p-toluenesulfonic acid, and toluene were fed into a 2L 4-necked flask equipped with a stirrer and a thermometer. 500g, heated up to 120°C for demethanolization reaction. Heating and distillation under reduced pressure were carried out at 230°C for 6 hours under reduced pressure to obtain 882 g of novolac resin (C'-2) as a pale yellow solid. 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. The GPC chart of the novolak resin (C'-2) is shown in Fig. 11 .

Comparative Example 2 Synthesis of Novolak Resin (C'-3) Feed 648g (6mol) of m-cresol, 432g (4mol) of p-cresol, 2.5g (0.2mol) of oxalic acid, and 492g of 42% formaldehyde into a 2L 4-necked flask equipped with a stirrer and a thermometer, raise the temperature to 100°C, and make it reaction. Dehydration was carried out at normal pressure, distillation was carried out to 200°C, and vacuum distillation was carried out at 230°C for 6 hours to obtain 736 g of novolak-type phenol resin (C'-3) as a pale yellow solid. The number average molecular weight (Mn) of the novolac resin (C'-3) was 1450, the weight average molecular weight (Mw) was 10316, and the polydispersity (Mw/Mn) was 7.116. The GPC chart of the novolak resin (C'-3) is shown in Fig. 12 .

」(2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三

)。Example 4 Preparation of photosensitive composition Dissolve 20 parts by mass of the esterified novolac type phenolic resin (Z-1) prepared in Example 1 in 75 parts by mass of propylene glycol monomethyl ether acetate (PGMEA). To the solution, 5 parts by mass of a photoacid generator was added and dissolved. The obtained solution was micro-filtered with a 0.1 micrometer polytetrafluoroethylene disk filter, and the photosensitive composition was prepared. In addition, the above-mentioned photoacid generator is "TME-three" manufactured by Sanwa Chemical Co., Ltd.

"(2-[2-(5-Methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-tri

).

The following evaluation was performed using the obtained photosensitive composition. The results are shown in Table 1. (1) Evaluation of Alkali Developability The photosensitive composition obtained by coating with a spinner is applied on a 5-inch silicon wafer to a thickness of about 1 μm, dried on a hot plate at 110°C for 60 seconds, and then coated on a silicon wafer. A resin film is formed on the circle. This operation was repeated to prepare a plurality of wafers for evaluation. The wafer for evaluation was immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and dried on a hot plate at 110° C. for 60 seconds after immersion. 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 wafers for evaluation were prepared, and one of them was used as a "non-exposed sample". The other was used as an "exposed sample" and was irradiated with ghi rays at 200 mJ/cm ² using a ghi ray lamp ("MULTILIGHT" manufactured by USHIO Electric Co., Ltd.), and then heat-treated at 110° C. for 120 seconds. Both the "non-exposed sample" and the "exposed sample" were immersed in an alkaline developer solution (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 alkali developability [ADR2(Å/s)]. The wafer for evaluation was dipped in an alkaline developer (15% sodium carbonate aqueous solution) for 60 seconds, and dried on a hot plate at 110° C. for 60 seconds after dipping. The film thickness before and after immersion in the developing solution was measured, and the value obtained by dividing the difference by 60 was regarded as alkali developability (ADR3(Å/s)). Two wafers for evaluation were prepared, and one was used as a "non-exposed sample". The other was irradiated with ghi rays at 200 mJ/cm ² using a ghi ray lamp ("MULTILIGHT" manufactured by USHIO Electric Co., Ltd.) as an "exposed sample", and then heat-treated at 110° C. for 120 seconds. Both the "non-exposed sample" and the "exposed sample" were immersed in an alkali developing solution (15% sodium carbonate aqueous solution) for 60 seconds, and then dried on a 110°C hot plate for 60 seconds. The film thickness of each sample before and after immersion in the developer solution was measured, and the value obtained by dividing the difference by 60 was taken as the alkali developability [ADR4(Å/s)].

(2) Evaluation of heat resistance The obtained photosensitive composition was coated on a 5-inch silicon wafer with a spinner 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 its glass transition temperature (Tg) was measured and evaluated. The glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC) ("Q100" manufactured by TA Instruments Co., Ltd.), under a nitrogen atmosphere, with a temperature range of -100 to 200°C and a temperature increase of 10°C/min. conditions. The case where the obtained glass transition temperature was 150° C. or higher was evaluated as “◯”, and the case where it was lower than 150° C. was evaluated as “×”.

Embodiment 5-6 and comparative example 3-5 Except having used the resin shown in Table 1 instead of the esterified novolac type phenol resin (Z-1), it carried out similarly to Example 4, prepared the photosensitive composition, and evaluated it. The results are shown in Table 1.

[Table 1] Example 4 Example 5 Example 6 Comparative example 3 Comparative example 4 Comparative Example 5 resin Z-1 Z-2 Z-3 C-1 C'-2 C'-3 Alkali developability ADR1 [Å/s] 12 twenty three 48 12000 3200 110 ADR2 [Å/s] 4300 5200 15000 16000 3500 320 ADR3 [Å/s] >1 >1 >1 530 >1 >1 ADR4 [Å/s] 320 410 580 620 >1 >1 heat resistance Tg [℃] 155 182 201 270 52 110 determination ○ ○ ○ ○ x x

As shown in the results in Table 1, the photosensitive composition of Comparative Example 3-5 was observed to be eluted with alkali in the stage before exposure, and it was found that it could not exhibit the function as a photosensitive composition. On the other hand, in the photosensitive composition of Examples 4-6, alkali elution was not observed in the stage before exposure, and it was found that alkali elution occurred by exposure, and a good development contrast was obtained. It is speculated that this is due to the acid of the photoacid generator, and the ester group of the esterified novolac type phenolic resin in Examples 1-3 is hydrolyzed to form a carboxyl group, thereby changing the polarity.

none.

Fig. 1 is a diagram showing a GPC chart of a carboxylic acid-containing phenolic trinuclear compound (A-1).

Fig. 2 is a diagram showing a ¹³ C-NMR chart of a carboxylic acid-containing phenolic trinuclear compound (A-1).

Fig. 3 is a graph showing a GPC chart of a novolak-type phenol resin (C-1).

Fig. 4 is a diagram showing a ¹³ C-NMR chart of a novolak-type phenol resin (C-1).

Fig. 5 is a graph showing a GPC chart of an esterified novolac type phenol resin (Z-1).

Fig. 6 is a graph showing a ¹³ C-NMR chart of an esterified novolak-type phenol resin (Z-1).

Fig. 7 is a graph showing a GPC chart of an esterified novolac type phenol resin (Z-2).

Fig. 8 is a graph showing a ¹³ C-NMR chart of an esterified novolak-type phenol resin (Z-2).

Fig. 9 is a graph showing a GPC chart of an esterified novolac type phenol resin (Z-3).

Fig. 10 is a graph showing a ¹³ C-NMR chart of an esterified novolak-type phenol resin (Z-3).

Fig. 11 is a graph showing a GPC chart of a novolak resin (C'-2).

Fig. 12 is a graph showing a GPC chart of a novolak resin (C'-3).

none.

Claims (8)

A photosensitive composition comprising a resin containing phenolic hydroxyl groups and a photoacid generator. The resin containing phenolic hydroxyl groups is a reaction product of a novolak-type phenolic resin (C) and an alcohol compound (X), wherein the novolak-type The phenolic resin (C) is based on the aromatic compound (A) represented by the following formula (1) and the aliphatic aldehyde (B) as the necessary reaction raw materials, and the reaction product is derived from the aromatic compound represented by the aforementioned formula (1). A reaction product in which part or all of the carboxyl groups in the novolak-type phenolic resin (C) of the compound (A) is esterified by reaction with the alcohol compound (X),

(In the aforementioned formula (1), _R1 and _R2 are independently independent, representing aliphatic hydrocarbon groups, alkoxy groups, aryl groups, aralkyl groups or halogen atoms with 1 to 9 carbon atoms; m, n and p are each Independent, representing an integer from 0 to 4; when R ₁ is a plural number, the R _1s of the plural numbers may be the same or different from each other; when R ₂ is a plural number, the R _2s of the plural numbers may be the same or different from each other ; _R3 represents a hydrogen atom, an aliphatic hydrocarbon group with 1 to 9 carbon atoms, or a structural site with one or more substituents selected from alkoxy, halogen and hydroxyl on the hydrocarbon group; _R4 represents a hydroxyl group, a carbon atom Aliphatic hydrocarbon groups, alkoxy groups or halogen atoms with numbers 1 to 9; when R ₄ is plural, the plural R ₄ may be the same or different from each other). The photosensitive composition according to claim 1, wherein the aromatic compound (A) is a reaction product of an alkyl-substituted phenol compound and at least one selected from the group consisting of carboxyl-containing aromatic aldehydes and carboxyl-containing aromatic ketones. The photosensitive composition according to claim 2, wherein the aforementioned 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 at least one selected from formaldehyde and paraformaldehyde. The photosensitive composition according to any one of claims 1 to 3, wherein the aforementioned alcohol compound (X) is one or more selected from aliphatic alcohols having 10 or less carbon atoms and ether alcohols having 10 or less carbon atoms. The photosensitive composition according to any one of Claims 1 to 3, wherein the esterification rate of the carboxyl groups of the novolak-type phenolic resin (C) is 5-70 mol%. The photosensitive composition according to any one of claims 1 to 3, wherein the number average molecular weight (Mn) of the aforementioned phenolic hydroxyl group-containing resin is in the range of 1,000 to 5,000. A resist film made of the photosensitive composition according to any one of claims 1 to 7.

Images