Iodobenzoyl sulfonate salt compounds and methods for producing the same

Abstract

An object is to provide a novel iodobenzoyl sulfonate salt compound and a method for producing the same. Another object is to provide a photoacid generator or the like using the iodobenzoyl sulfonate salt compound as an intermediate (raw material). 【Solution means】A compound represented by chemical formula (I). TIFF2026113427000066.tif23170 (In the formula, R 1 represents a hydrogen atom or -CF3. R 2 and R 3 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, or R 2 may be linked to R 3 to form a ring represented by formula (a) to formula (f). X represents an iodine atom.) TIFF2026113427000067.tif28170

Description

[Technical Field]

[0001] The present invention relates to iodobenzoyl sulfonate salt compounds and a method for producing the same. [Background technology]

[0002] In recent years, the miniaturization of patterns has been rapidly progressing in the manufacturing of semiconductor devices and liquid crystal display elements. To cope with this miniaturization, efforts are underway to shorten the wavelength (increase the energy) of exposure light sources and to explore new materials. For example, various photoacid generators have been investigated as materials for chemically amplified resists (Patent Document 1, etc.).

[0003] A photoacid generator is a material that generates acid upon light irradiation. By acting as a catalyst to remove protective groups in the resist resin component, the resin component is converted into a component soluble in alkaline developer. This mechanism allows for the formation of fine patterns in semiconductor photolithography by exposing the resist through a photomask, dissolving the resin component in the exposed area in the developer, while leaving the resin component in the unexposed area covered by the photomask intact.

[0004] As a photoacid generator, a photoacid generator in which an iodine atom has been introduced into the molecule has been proposed (Patent Document 2, etc.). By introducing an iodine atom into the molecule, a photoacid generator with high photodegradation efficiency can be made. However, introducing iodine atoms into the molecule presented a challenge: obtaining precursor compounds with high purity was difficult. In particular, high purity is crucial in the field of cutting-edge semiconductor photoresists, and there was a demand for intermediates that could be obtained with high purity. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2017-008014 [Patent Document 2] Japanese Patent Publication No. 2022-190871 [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention aims to provide a novel iodobenzoyl sulfonate salt compound and a method for producing the same. Furthermore, the present invention aims to provide a photoacid generator, etc., using the iodobenzoyl sulfonate salt compound as an intermediate (raw material). [Means for solving the problem]

[0007] As a result of diligent research, the inventors discovered that the compound represented by chemical formula (I) can solve the above-mentioned problems. Based on this finding, further research was conducted, leading to the completion of the present invention.

[0008] In other words, the present invention encompasses the following aspects. [1] A compound represented by chemical formula (I).

[0009] [ka] (In the formula, R 1 R represents a hydrogen atom or -CF3. 2 and R 3 R represents, either identically or differently, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, or R 2 R 3 They may be linked together to form the rings shown in equations (a) to (f). (X represents an iodine atom.)

[0010] [ka]

[0011] [2] The compound shown in [1] by chemical formula (Ia).

[0012] [ka] (where R 1 is the same as described above.)

[0013] A method for producing the compound according to [3], [1] or [2], comprising reacting tetraiodobenzoic acid represented by chemical formula (III) with a compound represented by chemical formula (IV), and then reacting a salt compound represented by chemical formula (V).

[0014]

Chemical formula

[0015] A method for producing the compound represented by chemical formula (II), comprising reacting the compound according to [1] or [2] with a compound represented by chemical formula (VII).

[0016]

Chemical formula

[0017] [5] The production method according to [4], wherein [A] n+ is a monovalent counter cation represented by formula (1) to formula (3).

[0018]

Chemical formula

[0019] A photoacid generator characterized by containing a compound produced by the manufacturing method described in [6][4] or [5].

[0020] [7] A compound represented by chemical formula (II).

[0021] [ka] (In the formula, R 1 represents a hydrogen atom or -CF3. X represents an iodine atom. n represents an integer between 1 and 2. [A] n+ (This represents an n-valent countercation.)

[0022] [8][A] n+ However, the compounds described in [7] are monovalent countercations represented by formulas (1) to (3). [ka] (In the formula, R 1a ~R 1c , R 2a ~R 2c These are the same or different halogen atoms, -CF3, -SO2R 5 -SF5, -CHR 11 CH2X 1 , alkyl groups with 1 to 10 carbon atoms, -OR 11 R represents -COOH, -NO2, a polymerizable group, or an acid-reactive group. 3a and R 3b These are the same or different halogen atoms, -CF3, -SO2R 6 -SF5, -CHR 11 CH2X 1 , alkyl groups with 1 to 10 carbon atoms, -OR 11 R represents -COOH, -NO2, a polymerizable group, or an acid-reactive group. 5R represents -CF3, -CF2CF3, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. 6 R represents an alkyl group having 1 to 10 carbon atoms, or a phenyl group. 11 X represents a hydrogen atom or a methyl group. 1 represents a halogen atom, a mesyloxy group (OMs), a tosyloxy group (OTs), or a trifluoromethanesulfonyloxy group (OTf). 1 represents a single join, -O-, -S-, -S(O)-, or -S(O)2-. m1~m3 represent integers from 0 to 5. p1 represents an integer from 0 to 5. p2 and p3 represent integers from 0 to 4. q1 and q2 represent integers from 0 to 5. When m1 is an integer from 2 to 5, multiple R 1a They may be the same or different, and when m2 is an integer between 2 and 5, multiple R 1b They may be the same or different, and when m3 is an integer between 2 and 5, multiple R 1c They may be the same or different. When p1 is an integer from 2 to 5, multiple R 2a They may be the same or different, and when p2 is an integer between 2 and 4, multiple R 2b They may be the same or different, and when p3 is an integer between 2 and 4, multiple R 2c They may be the same or different. When q1 is an integer from 2 to 5, multiple R 3a They may be the same or different, and when q2 is an integer between 2 and 5, multiple R 3b They may be the same or different. [Effects of the Invention]

[0023] The compound represented by chemical formula (I) of the present invention can be purified to high purity because it contains a pyridinium cation having an amino group. Therefore, the compound of the present invention is useful as an intermediate for photoacid generators. Furthermore, the photoacid generator produced from the compound of the present invention is useful, for example, as a photoacid generator for resists (especially chemically amplified resists) and as a photocationic polymerization initiator. [Modes for carrying out the invention]

[0024] The present invention will be described in detail below. 1. Compound of the present invention This invention relates to a compound represented by chemical formula (I) (hereinafter sometimes referred to as "the compound of the present invention"). The compound of the present invention includes the compounds represented by chemical formulas (I-1) to (I-3) described later.

[0025] [ka] (In the formula, R 1 R represents a hydrogen atom or -CF3. 2 and R 3 R represents, either identically or differently, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, or R 2 R 3 They may be linked together to form the rings shown in equations (a) to (f). (X represents an iodine atom.)

[0026] [ka]

[0027] R 2 and R 3 Examples of C1-C5 alkyl groups represented by include linear or branched C1-C5 alkyl groups, specifically methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, and the like.

[0028] The compound represented by chemical formula (I) includes the compounds represented by chemical formulas (I-1) to (I-3). Among the compounds represented by chemical formula (I), the compound represented by chemical formula (I-2) is preferred.

[0029] [ka] (In the formula, R 1 ~R 3 (This is the same as above.)

[0030] Examples of compounds represented by chemical formula (I-1) include those represented by chemical formulas (I-1-1) to (I-1-20). Examples of compounds represented by chemical formula (I-2) include those represented by chemical formulas (I-2-1) to (I-2-20). Examples of compounds represented by chemical formula (I-3) include those represented by chemical formulas (I-3-1) to (I-3-20).

[0031] [ka]

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] In the compound represented by chemical formula (I), the preferred substituents are as follows: R 1 However, it is preferable that it be a hydrogen atom or -CF3. R 2 and R 3is the same and is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. Or, R 2 is preferably one that forms a ring represented by the formula (a) by linking with R 3 . X is preferably bonded to the 2, 3, 4, and 6 positions of the phenyl group.

[0038] In addition, in the compound of the present invention, a compound represented by the chemical formula (I-a) is preferable.

[0039]

Chemical formula

[0040] Since the compound of the present invention can be purified to a high purity, it can be suitably used as an intermediate (raw material) of a photoacid generator.

[0041] 2. Method for synthesizing the compound of the present invention Examples of the method for synthesizing the compound of the present invention include the methods of synthesis methods (1) to (2).

[0042] <Synthesis method (1)> The compound of the present invention can be synthesized by reacting tetrayodobenzoic acid represented by the chemical formula (III) with a compound represented by the chemical formula (IV) (first step), and then reacting with a salt compound represented by the chemical formula (V) (second step) (see reaction scheme (A)).

[0043]

Chemical formula

[0045] Examples of tetraiodobenzoic acid represented by chemical formula (III) include tetraiodobenzoic acid represented by chemical formulas (III-1) to (III-3). Furthermore, tetraiodobenzoic acid represented by chemical formula (III-1) is a precursor of the compound represented by chemical formula (I-1), tetraiodobenzoic acid represented by chemical formula (III-2) is a precursor of the compound represented by chemical formula (I-2), and tetraiodobenzoic acid represented by chemical formula (III-3) is a precursor of the compound represented by chemical formula (I-3).

[0046] [ka]

[0047] Tetraiodobenzoic acid, represented by chemical formula (III), can be synthesized in accordance with the method described in Austrian Patent No. 209897, etc.

[0048] Examples of compounds represented by chemical formula (IV) include those represented by chemical formulas (IV-1) to (IV-2).

[0049] [ka]

[0050] The compound represented by chemical formula (IV) can be synthesized in accordance with the methods described in Japanese Patent Publication No. 2011-16746, Japanese Patent Publication No. 2018-13751, etc.

[0051] Examples of salt compounds represented by chemical formula (V) include those represented by chemical formulas (V-1) to (V-12).

[0052] [ka]

[0053] The salt compound represented by chemical formula (V) can be purchased as a commercially available reagent, or it can be synthesized according to the method described in, for example, Org. Lett., 2014, 16, 236-239.

[0054] In the first step of the reaction, the amount of compound represented by chemical formula (IV) used is preferably in an appropriate ratio within the range of 0.2 to 20 molars relative to the amount of tetraiodobenzoic acid represented by chemical formula (III).

[0055] In the first step of the reaction, a condensing agent (i), a basic catalyst (ii), and a reaction solvent (iii) may be used as appropriate, if necessary. Examples of condensing agents (i) include N,N′-dicyclohexylcarbodiimide, N,N′-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide, 1,1′-carbonyldi(1,2,4-triazole), and carbonyldiimidazole. These may be used alone or in combination of two or more. Furthermore, the amount of condensing agent (i) used is preferably in an appropriate proportion within the range of 0.2 to 20 times the molar amount of tetraiodobenzoic acid represented by chemical formula (III).

[0056] Examples of basic catalysts (ii) include tertiary amines such as trimethylamine, triethylamine, and tributylamine; aromatic amines such as pyridine, dimethylaminopyridine (DMAP), and pyrrolidinopyridine; diazabicyclononene (DBN); diazabicycloundecene (DBU); and imidazole. These may be used individually or in combination of two or more. Furthermore, the amount of basic catalyst (ii) used is preferably in an appropriate proportion within the range of 0.001 to 30 molars, and more preferably in the range of 1 to 10 molars, relative to the amount of tetraiodobenzoic acid represented by chemical formula (III).

[0057] The reaction solvent (iii) is not particularly limited as long as it does not inhibit the reaction, and includes, for example, ethers such as ethyl ether, isopropyl ether, tetrahydrofuran, 1,2-dimethoxyethane, methyltetrahydrofuran, methyltetrahydropyran, methyl-t-butyl ether, diisopropyl ether, diethyl ether, 1,4-dioxane, dimethoxyethane, tetrahydropyran, and propylene glycol monomethyl ether; Halogenated hydrocarbons such as methylene chloride, methylene bromide, 1,2-dichloroethane, chloroform, and bromoform; Examples include amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, and these can be combined as needed and used in appropriate amounts.

[0058] In the first step of the reaction, the reaction temperature is preferably set in the range of -80 to 60°C. The reaction time is set appropriately according to the set reaction temperature, but it is preferably set in the range of 30 minutes to 24 hours.

[0059] After the reaction in the first step is complete, the precursor of the compound of the present invention (hereinafter sometimes referred to as "precursor 1 of the present invention") can be extracted from the resulting reaction solution (reaction mixture) by means of, for example, concentration of the reaction solution by distillation of the reaction solvent or solvent extraction. Furthermore, if necessary, the product can be purified using methods such as washing with water, activated carbon treatment, silica gel chromatography, and recrystallization. Furthermore, the precursor 1 of the present invention may be subjected to the aforementioned concentration, extraction, and purification before being used in the second step, or it may be used in the second step as is, after the reaction in the first step is complete.

[0060] In the second step of the reaction, the amount of the salt compound represented by chemical formula (V) used is preferably in an appropriate proportion within the range of 1 to 30 molars relative to the amount of precursor 1 used in the present invention.

[0061] In the second step of the reaction, reaction solvent (iv) may be used as appropriate, if necessary. The reaction solvent (iv) is not particularly limited as long as it does not inhibit the reaction, and includes, for example, ethers such as ethyl ether, isopropyl ether, tetrahydrofuran, 1,2-dimethoxyethane, methyltetrahydrofuran, methyltetrahydropyran, methyl-t-butyl ether, diisopropyl ether, diethyl ether, 1,4-dioxane, dimethoxyethane, tetrahydropyran, and propylene glycol monomethyl ether; Hydrocarbons such as hexane and heptane; Aromatic hydrocarbons such as benzene and nitrobenzene; Halogenated hydrocarbons such as methylene chloride, methylene bromide, 1,2-dichloroethane, chloroform, and bromoform; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, pentanol, and hexanol; Esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, ethyl lactate, and propylene glycol monomethyl ether acetate; Examples include water, and these can be combined as needed, using appropriate amounts.

[0062] In this reaction, the reaction temperature is preferably set in the range of -80 to 60°C. The reaction time is set appropriately according to the set reaction temperature, but it is preferably set in the range of 30 minutes to 24 hours.

[0063] After the reaction is complete, the compound of the present invention, which is the target product, can be extracted from the resulting reaction solution by means of, for example, concentration of the reaction solution by distillation of the reaction solvent or solvent extraction. Furthermore, if necessary, purification can be carried out by means such as washing with water or the like, activated carbon treatment, silica gel chromatography, recrystallization, etc.

[0064] <Synthesis method (2)> The compound of the present invention can be synthesized by reacting a tetraiodobenzoic acid halide represented by Chemical Formula (VI) with a compound represented by Chemical Formula (IV) (first step), and then reacting a salt compound represented by Chemical Formula (V) (second step) (see Reaction Scheme (B)).

[0065] [Chemical formula] (In the formula, R 1 ~R 3 , X and [X a are the same as described above. X c represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.)

[0066] Examples of the tetraiodobenzoic acid halide represented by Chemical Formula (VI) include tetraiodobenzoic acid halides represented by Chemical Formulas (VI-1) to (VI-12). The tetraiodobenzoic acid halides represented by Chemical Formulas (VI-1) to (VI-4) are precursors of the compound represented by Chemical Formula (I-1), the tetraiodobenzoic acid halides represented by Chemical Formulas (VI-5) to (VI-8) are precursors of the compound represented by Chemical Formula (I-2), and the tetraiodobenzoic acid halides represented by Chemical Formulas (VI-9) to (VI-12) are precursors of the compound represented by Chemical Formula (I-3).

[0067] [Chemical formula]

[0068] The tetraiodobenzoic acid halide represented by Chemical Formula (VI) can be synthesized according to the method described in German Patent No. 1082369, etc.

[0069] The compound represented by chemical formula (IV) can be one of those exemplified in synthesis method (1). In the first step of the reaction, the amount of the compound represented by chemical formula (IV) used is preferably in an appropriate ratio within the range of 0.2 to 20 molars relative to the amount of the tetraiodobenzoic acid halide represented by chemical formula (VI).

[0070] In the first step of the reaction, a base (v) and reaction solvent (iii) may be used as appropriate, if necessary. As reaction solvent (iii), the one exemplified in synthesis method (1) can be used.

[0071] The bases (v) include trimethylamine, triethylamine, tributylamine, N,N-diisopropylethylamine, N-methylmorpholine, 1,5-diazabicyclo[4.3.0]nona-5-ene (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), pyridine, 4-(N,N-dimethylamino)pyridine, picoline, N,N-dimethylaniline, N,N-diethylaniline, imidazole, lithium hydride, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, carbon Examples include potassium phosphate, cesium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, trilithium phosphate, trisodium phosphate, tripotassium phosphate, tricesium phosphate, dilithium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dicesium hydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, cesium dihydrogen phosphate, lithium acetate, sodium acetate, potassium acetate, cesium acetate, lithium alkoxide (lithium methoxide, etc.), sodium alkoxide (sodium methoxide, sodium ethoxide, etc.), potassium alkoxide (t-butoxypotassium, etc.), etc. These may be used individually or in combination of two or more.

[0072] The amount of base (v) used is preferably in an appropriate proportion within the range of 1 to 20 molars, and more preferably in the range of 1 to 10 molars, relative to the amount of tetraiodobenzoic acid halide represented by chemical formula (VI).

[0073] In the first step of the reaction, the reaction temperature is preferably set in the range of -80 to 100°C. The reaction time is set appropriately according to the set reaction temperature, but it is preferably set in the range of 30 minutes to 24 hours.

[0074] After the reaction in the first step is complete, the precursor of the compound of the present invention (hereinafter sometimes referred to as "precursor 2 of the present invention") can be extracted from the resulting reaction solution (reaction mixture) by means of, for example, concentration of the reaction solution by distillation of the reaction solvent or solvent extraction. Furthermore, if necessary, the product can be purified using methods such as washing with water, activated carbon treatment, silica gel chromatography, and recrystallization. Furthermore, the precursor 2 of the present invention may be subjected to the aforementioned concentration, extraction, and purification before being used in the second step, or it may be used in the second step as is, after the reaction in the first step is complete.

[0075] As the salt compound represented by chemical formula (V), those exemplified in synthesis method (1) can be used. In the second step of the reaction, the amount of the salt compound represented by chemical formula (V) used is preferably in an appropriate proportion within the range of 1 to 30 molars relative to the amount of precursor 2 of the present invention used.

[0076] In the second step of the reaction, reaction solvent (iv) may be used as appropriate if necessary. The reaction solvent (iv) exemplified in synthesis method (1) can be used.

[0077] In this reaction, the reaction temperature is preferably set in the range of -80 to 60°C. The reaction time is set appropriately according to the set reaction temperature, but it is preferably set in the range of 30 minutes to 24 hours.

[0078] After the reaction is complete, the compound of the present invention, which is the target product, can be extracted from the resulting reaction solution by means of, for example, concentration of the reaction solution by distillation of the reaction solvent or solvent extraction. Furthermore, if necessary, the product can be purified using methods such as washing with water, activated carbon treatment, silica gel chromatography, and recrystallization.

[0079] 3. Synthesis method of the compound represented by chemical formula (II) The compounds of the present invention can be suitably used as intermediates (raw materials) for photoacid generators (compounds represented by chemical formula (II)). The compound represented by chemical formula (II) can be synthesized by reacting the compound of the present invention with the compound represented by chemical formula (VII) (see reaction scheme (C)).

[0080] [ka] (In the formula, R 1 ~R 3 And X are as described above. n represents an integer between 1 and 2. [A] n+ [X represents an n-valent countercation. b ] are halide ions, hydroxide ions, and trifluoromethanesulfonate (TfO - ), methanesulfonate (MsO - ), toluene sulfonate (TsO - ) Represents benzenesulfonate, benzoate, methoxide, ethoxide, t-butoxide, nitrite ion, or nitrate ion.

[0081] [X b Examples of halide ions represented by ] include fluoride ions, chloride ions, bromide ions, or iodide ions.

[0082] In the compound represented by chemical formula (II), [A] n+ It is preferable that is a monovalent countercation represented by formulas (1) to (3).

[0083] [ka] (In the formula, R 1a ~R 1c , R 2a ~R 2c These are the same or different halogen atoms, -CF3, -SO2R 5 -SF5, -CHR 11 CH2X 1 , alkyl groups with 1 to 10 carbon atoms, -OR 11 R represents -COOH, -NO2, a polymerizable group, or an acid-reactive group. 3a and R 3b These are the same or different halogen atoms, -CF3, -SO2R 6 -SF5, -CHR 11 CH2X 1 , alkyl groups with 1 to 10 carbon atoms, -OR 11 R represents -COOH, -NO2, a polymerizable group, or an acid-reactive group. 5 R represents -CF3, -CF2CF3, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. 6 R represents an alkyl group having 1 to 10 carbon atoms, or a phenyl group. 11 X represents a hydrogen atom or a methyl group. 1 represents a halogen atom, a mesyloxy group (OMs), a tosyloxy group (OTs), or a trifluoromethanesulfonyloxy group (OTf). 1 represents a single join, -O-, -S-, -S(O)-, or -S(O)2-. m1~m3 represent integers from 0 to 5. p1 represents an integer from 0 to 5. p2 and p3 represent integers from 0 to 4. q1 and q2 represent integers from 0 to 5. When m1 is an integer from 2 to 5, multiple R 1a They may be the same or different, and when m2 is an integer between 2 and 5, multiple R 1b They may be the same or different, and when m3 is an integer between 2 and 5, multiple R 1c They may be the same or different. When p1 is an integer from 2 to 5, multiple R 2a They may be the same or different, and when p2 is an integer between 2 and 4, multiple R 2bThey may be the same or different, and when p3 is an integer between 2 and 4, multiple R 2c They may be the same or different. When q1 is an integer from 2 to 5, multiple R 3a They may be the same or different, and when q2 is an integer between 2 and 5, multiple R 3b They may be the same or different.

[0084] R 1a ~R 1c , R 2a ~R 2c , R 3a ~R 3b and X 1 Examples of halogen atoms represented by include fluorine, chlorine, bromine, and iodine.

[0085] R 1a ~R 1c , R 2a ~R 2c , R 3a ~R 3b , R 5 and R 6 Examples of C1-C10 alkyl groups represented by include linear, branched, or cyclic C1-C10 alkyl groups, specifically methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl, 1-adamantyl, and 2-adamantyl groups, among which methyl, t-butyl, cyclohexyl, and 1-adamantyl groups are preferred. The presence of an alkyl group is expected to improve compatibility with polymers having structural units containing acid-reactive groups.

[0086] R 1a ~R 1c , R 2a ~R 2c , R 3a ~R 3b Polymerizable groups include groups having polymerizable functional groups (for example, carbon-carbon double bonds). Examples of polymerizable groups include the groups represented by formulas (S-1) to (S-4).

[0087] [ka] (In the formula, R 11 (where represents a hydrogen atom or a methyl group, and Y represents a single bond or an alkylene group with 1 to 5 carbon atoms.)

[0088] Examples of alkylene groups having 1 to 5 carbon atoms represented by Y include methylene groups, ethylene groups (-CH2CH2- and -CH(CH3)-), propylene groups (-CH2CH2CH2-, -CH2CH(CH3)-, and -CH(CH3)CH2-), butylene groups (-CH2CH2CH2CH2- and -CH2C(CH3)2-), and pentylene groups (-CH2CH2CH2CH2CH2- and -CH2CH2C(CH3)2-).

[0089] R 1a ~R 1c , R 2a ~R 2c , R 3a ~R 3b The acid-reactive group indicated by the symbol preferably has a structure in which a polar group is protected by a group that reacts with the action of an acid (for example, a group that decomposes and is eliminated (leaving group)). Examples of polar groups include acidic groups (groups that dissociate in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide), such as carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups, as well as alcoholic hydroxyl groups. R 1a ~R 1c , R 2a ~R 2c , R 3a ~R 3b Examples of acid-reactive groups represented by these formulas include the groups shown in formulas (R-1) to (R-7).

[0090] [ka] (In the formula, Y is the same as above. R 12 ~R 14 R represents, either identically or differently, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an aromatic group having 4 to 18 carbon atoms, or R 12 R 13 and / or R 14 They may be linked together to form an aliphatic hydrocarbon ring with 3 to 20 carbon atoms, together with the carbon atoms to which they are bonded. 15 and R 16 R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, either identical or different. 17 represents an alkyl group having 1 to 20 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. The -CH2- contained in the alkyl group, aliphatic hydrocarbon ring, and alicyclic hydrocarbon group may be replaced with -C(O)-, -O-, or -S-. a represents an integer from 0 to 4. However, in formulas (R-1), (R-3), and (R-5) to (R-7), R 12 ~R 14 (Except when all atoms are hydrogen atoms.)

[0091] R 12 ~R 14 , R 17 Examples of C1-C20 alkyl groups represented by include linear, branched, or cyclic C1-C20 alkyl groups, specifically methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl, octyl, octadecyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1-adamantyl, 2-adamantyl, decahydronaphthyl, decahydrodimethanonaphthyl, norbornyl, etc.

[0092] R 15 and R 16Examples of C1-C6 alkyl groups represented by include linear or branched C1-C6 alkyl groups, specifically methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, and the like.

[0093] R 12 ~R 14 Examples of C2-C8 alkenyl groups represented by include linear, branched, or cyclic C2-C8 alkenyl groups, specifically including ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, t-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, nonenyl, norborneyl, etc.

[0094] R 12 ~R 14 Aromatic groups with 4 to 18 carbon atoms, as shown, include monocyclic or bicyclic or multicyclic aromatic groups (aryl groups, heteroaryl groups, etc.). Examples include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl groups, and aryl groups such as furyl groups.

[0095] R 12 And, R 13 and / or R 14 Examples of aliphatic hydrocarbon rings having 3 to 20 carbon atoms that are formed by the linkage of these atoms together with the carbon atoms to which they are bonded include monocyclic or two or more saturated or unsaturated alicyclic hydrocarbon rings. Examples include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, cyclooctane rings, adamantane rings, decahydronaphthalene rings, decahydrodimethanonaphthalene rings, norbornane rings, norbornene rings, etc. Furthermore, examples of rings in which the -CH2- group in an aliphatic hydrocarbon ring is replaced by -C(O)-, -O-, and -S- include tetrahydrofuran rings, (methoxymethyl)tetrahydrofuran rings, tetrahydropyran rings, oxatian rings, and oxabicycloheptane rings.

[0096] R 17 Examples of alicyclic hydrocarbon groups having 3 to 20 carbon atoms, as shown by , include monocyclic or two or more saturated or unsaturated alicyclic hydrocarbon groups. Examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, 1-adamantyl group, 2-adamantyl group, decahydronaphthyl group, decahydrodimethanonaphthyl group, norbornyl group, norbornenyl ring, etc. Furthermore, examples of groups in which the -CH2- contained in an alicyclic hydrocarbon group is replaced with -C(O)-, -O-, and -S- include the tetrahydrofuranyl group, (methoxymethyl)tetrahydrofuranyl group, tetrahydropyranyl group, oxathianyl group, and oxabicycloheptyl group.

[0097] Examples of compounds represented by chemical formula (VII) include those represented by chemical formulas (VII-1-1) to (VII-3-33).

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] [ka]

[0107] The compound represented by chemical formula (VII) can be used by purchasing commercially available reagents, as well as by referring to Japanese Patent Publication No. 2017-008014, International Publication No. 2024 / 029354, J.Am.Chem.Soc.(1990),112(16),6004-6015, J.Org.Chem.(1988),5571-5573, Japanese Patent Publication No. 2020-152718, J.Org.Chem.(2017),82(15),7708-7719, International Publication No. 2020 / 094673, J.Org.Chem.(2011),76(13),5240-5246, CCS Chemistry(2021),3(7),1940-1948, and Tetrahedron. It can be synthesized in accordance with the methods described in Letters (2001), 42(5), 855-857, European Patent Application Publication No. 972761, J. Org. Chem. (2019), 84(9), 5684-5694, etc.

[0108] The amount of the compound represented by chemical formula (VII) used is preferably in an appropriate proportion within the range of 1 to 20 molars relative to the amount of the compound of the present invention used.

[0109] In carrying out this reaction, reaction solvent (iv) may be used as appropriate if necessary. As reaction solvent (iv), the one described in section 2. Method for synthesizing the compound of the present invention above can be used.

[0110] In this reaction, the reaction temperature is preferably set in the range of -80 to 60°C. The reaction time is set appropriately according to the set reaction temperature, but it is preferably set in the range of 30 minutes to 24 hours.

[0111] After the reaction is complete, the target compound represented by chemical formula (II) can be extracted from the resulting reaction solution by means of, for example, concentration of the reaction solution by distillation of the reaction solvent or solvent extraction. Furthermore, if necessary, the product can be purified using methods such as washing with water, activated carbon treatment, silica gel chromatography, and recrystallization.

[0112] 4. Compounds represented by chemical formula (II) Examples of compounds represented by chemical formula (II) include those represented by chemical formulas (II-1-1) to (II-3-38).

[0113] [ka]

[0114] [ka]

[0115] [ka]

[0116] [ka]

[0117] [ka]

[0118] [ka]

[0119]

change

[0120]

change

[0121]

change

[0122]

change

[0123]

change

[0124]

change

[0125]

change

[0126]

change

[0127]

change

[0128]

change

[0129] In the compounds represented by chemical formula (II), compounds represented by chemical formulas (II-1) to (II-3) are preferred.

[0130] [ka] (In the formula, R 1 , R 1a ~R 1c , R 2a ~R 2c , R 3a ~R 3b , X, Y 1 (m1~m3, p1~p3, q1 and q2 are the same as described above.)

[0131] In the compound represented by chemical formula (II-1), preferred substituents are as follows: R 1 However, it is preferable that it be a hydrogen atom or -CF3. It is preferable that X is bonded to the 2, 3, 4, and 6 positions of the phenyl group. R 1a ~R 1c However, they may be the same or different halogen atoms (preferably fluorine or iodine atoms), -CF3, -SO2R 5 , -OR 11 It is preferable that the group is a -COOH group, a polymerizable group, or an acid-reactive group. R 5 However, -CF3 is preferable. R 11 However, it is preferable that it be a hydrogen atom or a methyl group. It is preferable that m1 to m3 are the same or different integers between 0 and 5, and more preferably between 0 and 2. It is also preferable that at least one of m1 to m3 is an integer between 1 and 2.

[0132] In the compound represented by chemical formula (II-2), preferred substituents are as follows: R 1 However, it is preferable that it be a hydrogen atom or -CF3. It is preferable that X is bonded to the 2, 3, 4, and 6 positions of the phenyl group. R 2a ~R 2c However, they may be the same or different halogen atoms (preferably fluorine or iodine atoms), -CF3, -SO2R 5 , -OR 11 It is preferable that the group is a -COOH group, a polymerizable group, or an acid-reactive group. R 5 However, -CF3 is preferable. R 11 However, it is preferable that it be a hydrogen atom or a methyl group. Y 1 However, it is preferable that the bond be a single bond, -O-, -S-, -S(O)-, or -S(O)2-, and more preferably a single bond. It is preferable that p1 is an integer between 0 and 5, and more preferably an integer between 0 and 2. It is preferable that p2 and p3 are the same or different integers between 0 and 4, and more preferably between 0 and 2. It is also preferable that at least one of p1 to p3 is an integer between 1 and 2.

[0133] In the compound represented by chemical formula (II-3), preferred substituents are as follows: R 1 However, it is preferable that it be a hydrogen atom or -CF3. It is preferable that X is bonded to the 2, 3, 4, and 6 positions of the phenyl group. R 3a and R 3b However, they may be the same or different halogen atoms (preferably fluorine or iodine atoms), -CF3, -OR 11 It is preferable that the group is a -COOH group, a polymerizable group, or an acid-reactive group. R 11 However, it is preferable that it be a hydrogen atom or a methyl group. Preferably, q1 and q2 are the same or different integers between 0 and 5, and more preferably between 0 and 2. Furthermore, it is preferable that at least one of q1 and q2 is an integer between 1 and 2.

[0134] [A] n+Examples of the n-valent counter cation shown by [[ID=]] are not particularly limited as long as it can be a counter cation of tetraiodobenzoyloxy-1,1-difluoroethane-1-sulfonic acid anion or tetraiodobenzoyloxy-1,1,3,3,3-pentafluoropropane-1-sulfonic acid anion.

[0135] [A] n+ Examples of the n-valent counter cation shown by [[ID=]] include onium cations and the like. [A] n+ When [[ID=]] is a monovalent (n = 1) cation (i.e., A + ), examples of A + include those shown in the following documents. · International Publication No. 2023 / 162907 ([Chemical Formula 49] to [Chemical Formula 55]) · Japanese Patent Application Laid-Open No. 2023-090803 ([Chemical Formula 20]) · Japanese Patent Application Laid-Open No. 2023-116251 ([Chemical Formula 25], [Chemical Formula 26]) · Japanese Patent Application Laid-Open No. 2023-116474 ([Chemical Formula 5], [Chemical Formula 7], [Chemical Formula 8], [Chemical Formula 25]) · Japanese Patent Application Laid-Open No. 2023-117394 (counter cations in

[0040] and

[0045] ) · Japanese Patent Application Laid-Open No. 2023-118096 (

[0132] ,

[0180] ) · Japanese Patent Application Laid-Open No. 2023-131576 ([Chemical Formula 11] to [Chemical Formula 17]) · Japanese Patent Application Laid-Open No. 2023-131926 ([Chemical Formula 58] to [Chemical Formula 64]) · Japanese Patent Application Laid-Open No. 2023-132684 ([Chemical Formula 23] to [Chemical Formula 46]) · Japanese Patent Application Laid-Open No. 2023-133148 ([Chemical Formula 40] to [Chemical Formula 63]) · Japanese Patent Application Laid-Open No. 2023-145385 ([Chemical Formula 19] to [Chemical Formula 21]) · Japanese Patent Application Laid-Open No. 2023-145543 ([Chemical Formula 21] to [Chemical Formula 23]) · Japanese Patent Application Laid-Open No. 2023-152629 ([Chemical Formula 66] to [Chemical Formula 91])

[0136] [A] n+ When [[ID=]] is a divalent (n = 2) cation (i.e., A 2+ ), A2+ Examples include those shown in the following literature. Japanese Patent Publication No. 2021-151992 (

[0011] ~

[0013] ) Japanese Patent Publication No. 2018-004776 ([Chemical Formula 60], [Chemical Formula 61]) • Chinese Patent Application Publication No. 111694215 ([Compound 13] to [Compound 20] countercations) • Japanese Patent Publication No. 2003-076010 (counter-cations of [I-1] to [I-51])

[0137] 5. Photoacid generator and resist composition containing the compound represented by chemical formula (II) The compound represented by chemical formula (II) is expected to have high photosensitivity to active energy rays such as EUV (extreme ultraviolet light), EB (electron beam), and X-rays, and is therefore suitable for use as a photoacid generator in resist compositions. Furthermore, the resist composition containing the compound represented by chemical formula (II) may contain, as optional, other photoacid generators, acid diffusion control agents, other resins, solvents, additives, etc., in addition to the compound represented by chemical formula (II) and a polymer having a structural unit containing an acid-reactive group. In the present invention, the resist composition refers to the mixture in its state before curing.

[0138] [Polymers having structural units containing acid-reactive groups] The polymer having an acid-reactive group in a resist composition containing the compound represented by chemical formula (II) is not particularly limited as long as it is one that is commonly used as a material for resist compositions. Acid-reactive groups are preferably structures in which a polar group is protected by a group that reacts with an acid (for example, a group that decomposes and is eliminated (a leaving group)). Examples of polar groups include acidic groups (groups that dissociate in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide), such as carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups, as well as alcoholic hydroxyl groups.

[0139] Examples of acid-reactive groups include the aforementioned R 1a ~R 1c , R 2a ~R 2c , R 3a ~R 3b The acid-reactive groups shown can be selected from those exemplified by the formulas (R-1) to (R-7) mentioned above.

[0140] Examples of polymers having structural units containing acid-reactive groups include those containing structural units (or monomers) shown in the following literature. • International Publication No. 2023 / 162907 ([Chemistry 2]~[Chemistry 36]) • Japanese Patent Publication No. 2023-016886 ([Chemical Formula 28], [Chemical Formula 29], [Chemical Formula 49]~[Chemical Formula 53]) • Japanese Patent Publication No. 2023-116251 ([Chemical Formula 8]~[Chemical Formula 16]) • Japanese Patent Publication No. 2023-116474 ([Chemical Formula 13]~[Chemical Formula 20]) Japanese Patent Publication No. 2023-117394 (

[0091] ~

[0188] ) Japanese Patent Publication No. 2023-118096 (

[0021] ~

[0120] ) Japanese Patent Publication No. 2023-131576 (

[0101] ~

[0216] ) • Japanese Patent Publication No. 2023-132684 ([Chemical Formulas 51~[Chemical Formulas 63]) • Japanese Patent Publication No. 2023-133148 ([Chemical Formula 114]~[Chemical Formula 123])

[0141] Polymers having structural units containing acid-reactive groups are obtained by heating monomers having the aforementioned structural units in an organic solvent together with a radical polymerization initiator to polymerize them. In this polymerization, the compound represented by chemical formula (II), other photoacid generators and acid diffusion control agents described later can be used.

[0142] Examples of organic solvents include toluene, benzene, tetrahydrofuran (THF), diethyl ether, and dioxane. Examples of radical polymerization initiators include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. The polymerization temperature is preferably 50-80°C. The reaction time is preferably 2 to 100 hours, more preferably 5 to 20 hours.

[0143] Polymers having structural units containing acid-reactive groups have a polystyrene-based weight-average molecular weight (Mw) of preferably 1,000 to 500,000, more preferably 2,000 to 30,000, as determined by gel permeation chromatography (GPC) using THF as a solvent. When Mw is within this range, the heat resistance and solubility in alkaline developers of the resist film are good.

[0144] In polymers having structural units containing acid-reactive groups, a broad molecular weight distribution (Mw / Mn) may result in the presence of low-molecular-weight and high-molecular-weight polymers, potentially leading to the appearance of foreign matter on the pattern or deterioration of the pattern shape after exposure. As the pattern rules become finer, the influence of Mw and Mw / Mn tends to increase. Therefore, to obtain a resist composition suitable for fine pattern dimensions, it is preferable that the Mw / Mn of the polymer having structural units containing acid-reactive groups be narrowly dispersed, specifically between 1.0 and 2.0, and particularly between 1.0 and 1.5. Furthermore, a polymer having a structural unit containing an acid-reactive group may include two or more polymers with different composition ratios, Mw, and Mw / Mn.

[0145] [Compounds represented by chemical formula (II)] The compound represented by chemical formula (II) has the property of generating acid upon irradiation with light. Therefore, the compound represented by chemical formula (II) functions as a photoacid generator.

[0146] In a resist composition containing the compound represented by chemical formula (II), there are no particular restrictions on the amount of the compound represented by chemical formula (II), but it is 1 to 10 parts by weight, preferably 2 to 5 parts by weight, per 100 parts by weight of polymer having a structural unit containing an acid-reactive group.

[0147] [Other photoacid generators] A resist composition containing the compound represented by chemical formula (II) may also use a photoacid generator other than the compound represented by chemical formula (II) (another photoacid generator). Other photoacid generators that are widely known can be used, for example, salts in which cations and anions are paired, as shown in the following literature. <Cation> • International Publication No. 2023 / 162907 ([Chemistry 49]~[Chemistry 55]) Japanese Patent Publication No. 2023-090803 ([Chemical Formula 20]) • Japanese Patent Publication No. 2023-116251 ([Chemical Formula 25], [Chemical Formula 26]) Japanese Patent Publication No. 2023-116474 ([Chemical Formula 5], [Chemical Formula 7], [Chemical Formula 8], [Chemical Formula 25]) Japanese Patent Publication No. 2023-117394 (

[0040] ,

[0045] ) Japanese Patent Publication No. 2023-118096 (

[0132] ,

[0180] ) • Japanese Patent Publication No. 2023-131576 ([Chemical Formula 11]~[Chemical Formula 17]) Japanese Patent Publication No. 2023-131926 ([Chemical Formulas 58~[Chemical Formulas 64]) • Japanese Patent Publication No. 2023-132684 ([Chemical Formulas 23]~[Chemical Formulas 46]) Japanese Patent Publication No. 2023-133148 ([Chemical Formula 40]~[Chemical Formula 63]) • Japanese Patent Publication No. 2023-145385 ([Chemical Formula 19]~[Chemical Formula 21]) • Japanese Patent Publication No. 2023-145543 ([Chemical Formula 21]~[Chemical Formula 23]) • Japanese Patent Publication No. 2023-152629 ([Chemical Formulas 66]~[Chemical Formulas 91]) <Anion> • International Publication No. 2023 / 162907 ([Chemical Engineering 38]~[Chemical Engineering 46]) Japanese Patent Publication No. 2023-116251 ([Chemical Formula 27]) Japanese Patent Publication No. 2023-116474 ([Chemical Formula 29]) Japanese Patent Publication No. 2023-118096 (

[0175] ,

[0176] ) • Japanese Patent Publication No. 2023-132684 ([Chemical Formulas 67~[Chemical Formulas 78]) • Japanese Patent Publication No. 2023-133148 ([Chemical Formulas 77]~[Chemical Formulas 80]) • Japanese Patent Publication No. 2023-135555 (Anion pair of [Chemical Formula 102] to [Chemical Formula 105]) Japanese Patent Publication No. 2023-145543 ([Chemical Formula 24], [Chemical Formula 25])

[0148] The amount of other photoacid generators in a resist composition containing the compound represented by chemical formula (II) is not particularly limited, but is 0 to 10 parts by weight, preferably 0 to 5 parts by weight, per 100 parts by weight of polymer having structural units containing acid-reactive groups.

[0149] [Acid diffusion control agent] A resist composition containing the compound represented by chemical formula (II) may also contain an acid diffusion control agent. Examples of acid diffusion control agents include salts in which cations and anions are paired, as shown in the following literature. <Cation> • International Publication No. 2023 / 162907 ([Chemistry 49]~[Chemistry 55]) Japanese Patent Publication No. 2023-090803 ([Chemical Formula 20]) • Japanese Patent Publication No. 2023-116251 ([Chemical Formula 25], [Chemical Formula 26]) Japanese Patent Publication No. 2023-116474 ([Chemical Formula 5], [Chemical Formula 7], [Chemical Formula 8], [Chemical Formula 25]) Japanese Patent Publication No. 2023-117394 (

[0040] ,

[0045] ) Japanese Patent Publication No. 2023-118096 (

[0132] ,

[0180] ) • Japanese Patent Publication No. 2023-131576 ([Chemical Formula 11]~[Chemical Formula 17]) Japanese Patent Publication No. 2023-131926 ([Chemical Formulas 58~[Chemical Formulas 64]) • Japanese Patent Publication No. 2023-132684 ([Chemical Formulas 23]~[Chemical Formulas 46]) Japanese Patent Publication No. 2023-133148 ([Chemical Formula 40]~[Chemical Formula 63]) • Japanese Patent Publication No. 2023-145385 ([Chemical Formula 19]~[Chemical Formula 21]) • Japanese Patent Publication No. 2023-145543 ([Chemical Formula 21]~[Chemical Formula 23]) • Japanese Patent Publication No. 2023-152629 ([Chemical Formulas 66]~[Chemical Formulas 91]) <Anion> • International Publication No. 2023 / 157455 ([Chemical Formula 25], [Chemical Formula 31], [Chemical Formula 32]) • International Publication No. 2023 / 157456 ([Chemistry 29]) • International Publication No. 2023 / 171527 (

[0355] ~

[0358] , [Chemical 76]~[Chemical 78]) • Japanese Patent Publication No. 2023-116474 ([Chemical Formula 38], [Chemical Formula 39]) • Japanese Patent Publication No. 2023-136980 ([Chemical Formulas 31]~[Chemical Formulas 34]) Japanese Patent Publication No. 2023-145543 ([Chemical Formula 69] for anion pair)

[0150] The amount of acid diffusion control agent in a resist composition containing the compound represented by chemical formula (II) is not particularly limited, but is 0 to 10 parts by weight, preferably 0 to 5 parts by weight, per 100 parts by weight of polymer having structural units containing acid-reactive groups.

[0151] [Other resins] The resist composition containing the compound represented by chemical formula (II) may optionally contain other resins. Other resins include resins containing fluorine atoms (hereinafter sometimes referred to as "fluorine-containing resins"). When the other resin is a fluorine-containing resin, it is preferable that the partial structure includes an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom. Other resins include, for example, those containing structural units (or monomers) as shown in the following literature. • Japanese Patent Publication No. 2023-133148 ([Chemical Formula 118]~[Chemical Formula 120]) • Japanese Patent Publication No. 2023-132684 ([Chemical Formulas 57~[Chemical Formulas 60]) • Japanese Patent Publication No. 2023-117394 (

[0142] ~

[0171] ) Japanese Patent Publication No. 2023-016886 ([Chemical Formula 28], [Chemical Formula 52], [Chemical Formula 53])

[0152] [solvent] A resist composition containing the compound represented by chemical formula (II) may optionally contain a solvent. Any solvent that can dissolve each component used to form a homogeneous solution is acceptable, and any solvent conventionally known for use in chemically amplified resist compositions can be appropriately selected and used. Examples of solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; Monohydric alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; Polyhydric alcohols (glycols) such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; Glycol monoethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), or dipropylene glycol monomethyl ether; Glycol diethers such as ethylene glycol dimethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; Cyclic ethers such as dioxanes; Alkyl monocarboxylates such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, tert-butyl acetate, methyl pyruvate, ethyl pyruvate, tert-butyl propionate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; Glycol monoesters such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; Glycol ether esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monotert-butyl ether acetate; Lactones such as γ-butyrolactone; Aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenethole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene; Examples include dimethyl sulfoxide (DMSO). These can be used individually or in combination of two or more. Among them, PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are preferred.

[0153] [Additives] A resist composition containing the compound represented by chemical formula (II) may optionally contain additives. Examples of additives include surfactants, dissolution inhibitors, crosslinking agents, water-repellent enhancers, acetylene alcohols, plasticizers, stabilizers, colorants, anti-halation agents, and dyes.

[0154] Examples of surfactants include those described in Japanese Patent Publication No. 2008-111103 (

[0165] ,

[0166] ). By adding these surfactants, the coatability of the resist composition can be further improved or controlled. The amount of surfactant in a resist composition containing the compound represented by chemical formula (II) is not particularly limited, but is 0 to 10 parts by weight per 100 parts by weight of polymer having a structural unit containing an acid-reactive group.

[0155] Examples of dissolution inhibitors (dissolution suppressants) include compounds having a molecular weight of 100 to 1000, preferably 150 to 800, and containing two or more phenolic hydroxyl groups in the molecule, in which the hydrogen atoms of the phenolic hydroxyl groups are replaced by acid-unstable groups in a proportion of 0 to 100 mol% overall, or compounds containing a carboxyl group in the molecule, in which the hydrogen atoms of the carboxyl group are replaced by acid-unstable groups in an average proportion of 50 to 100 mol overall. Specifically, examples include compounds in which the hydrogen atoms of the hydroxyl or carboxyl groups of bisphenol A, trisphenol, phenolphthalein, cresol novolac, naphthalenecarboxylic acid, adamantanecarboxylic acid, and cholic acid are replaced by acid-unstable groups, and those described in Japanese Patent Application Publication No. 2008-122932 (

[0155] to

[0178] ).

[0156] When a resist composition containing the compound represented by chemical formula (II) is of the positive type, incorporating these dissolution inhibitors (dissolution suppressants) can further increase the difference in dissolution rates between the exposed and unexposed areas, thereby further improving the resolution. The amount of dissolution inhibitor (dissolution suppressant) in a resist composition containing the compound represented by chemical formula (II) is not particularly limited, but is 0 to 50 parts by weight, preferably 0 to 40 parts by weight, per 100 parts by weight of polymer having a structural unit containing an acid-reactive group.

[0157] Examples of crosslinking agents include epoxy compounds, melamine compounds, guanamine compounds, glycoluryl compounds or urea compounds, isocyanate compounds, azide compounds, and compounds containing double bonds such as alkenyloxy groups, which are substituted with at least one group selected from methylol, alkoxymethyl, and acyloxymethyl groups. These may be added or introduced as pendant groups into the polymer side chains. Compounds containing hydroxyl groups can also be used as crosslinking agents. When a resist composition containing the compound represented by chemical formula (II) is of the positive type, the dissolution rate of the exposed area can be reduced by incorporating a crosslinking agent, thereby obtaining a negative type pattern.

[0158] Examples of epoxy compounds include tris(2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, and triethylolethane triglycidyl ether.

[0159] Examples of melamine compounds include hexamethylmelamine, hexamethoxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylmelamine are methoxymethylated or mixtures thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylmelamine are acyloxymethylated or mixtures thereof.

[0160] Examples of guanamine compounds include tetramethylolguanamine, tetramethoxymethylguanamine, compounds in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated or mixtures thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, compounds in which 1 to 4 methylol groups of tetramethylolguanamine are acyloxymethylated or mixtures thereof.

[0161] Examples of glycoluryl compounds include tetramethylol glycoluryl, tetramethoxy glycoluryl, tetramethoxymethyl glycoluryl, compounds in which 1 to 4 methylol groups of tetramethylol glycoluryl are methoxymethylated or mixtures thereof, compounds in which 1 to 4 methylol groups of tetramethylol glycoluryl are acyloxymethylated or mixtures thereof. Examples of urea compounds include tetramethylolurea, tetramethoxymethylurea, compounds in which 1 to 4 methylol groups of tetramethylolurea are methoxymethylated or mixtures thereof, tetramethoxyethylurea, and the like.

[0162] Examples of isocyanate compounds include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.

[0163] Examples of azide compounds include 1,1′-biphenyl-4,4′-bisazide, 4,4′-methylidenebisazide, and 4,4′-oxybisazide.

[0164] Examples of compounds containing an alkenyloxy group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol 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, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, and trimethylolpropane trivinyl ether.

[0165] The amount of crosslinking agent in a resist composition containing the compound represented by chemical formula (II) is not particularly limited, but is 0 to 50 parts by weight, preferably 0 to 40 parts by weight, per 100 parts by weight of polymer having structural units containing acid-reactive groups.

[0166] The water-repellency improving agent is not particularly limited as long as it dissolves in alkaline developers or organic solvent developers. Examples include polymers containing alkyl fluoride, polymers containing 1,1,1,3,3,3-hexafluoro-2-propanol residues of a specific structure, and those described in Japanese Patent Publication No. 2007-297590 and Japanese Patent Publication No. 2008-111103. By incorporating these water-repellency improving agents, the water repellency of the resist film surface is improved, making it usable in immersion lithography without a topcoat. The amount of water-repellent enhancer in a resist composition containing the compound represented by chemical formula (II) is not particularly limited, but is 0 to 20 parts by weight, preferably 0 to 10 parts by weight, per 100 parts by weight of a polymer having a structural unit containing an acid-reactive group.

[0167] Examples of acetylene alcohols include those described in Japanese Patent Publication No. 2008-122932 (

[0179] to

[0182] ). The amount of acetylene alcohols in a resist composition containing the compound represented by chemical formula (II) is not particularly limited, but is 0 to 5 parts by weight per 100 parts by weight of a polymer having a structural unit containing an acid-reactive group.

[0168] [Method for preparing a resist composition] A resist composition containing the compound represented by chemical formula (II) can be prepared, for example, by mixing the compound represented by chemical formula (II), a polymer having a structural unit containing an acid-reactive group, and, if necessary, other photoacid generators, acid diffusion control agents, other resins, solvents, and additives in predetermined proportions. Furthermore, the resist composition containing the compound represented by chemical formula (II) is preferably filtered after mixing using a filter with a pore size of approximately 0.05 μm to 0.2 μm. The solid content concentration of the resist composition containing the compound represented by chemical formula (II) is usually 0.1% to 50% by mass, preferably 0.5% to 30% by mass, and more preferably 1% to 20% by mass.

[0169] 6. Method for forming a resist pattern When a resist composition containing the compound represented by chemical formula (II) is used in the manufacture of various integrated circuits, known lithography techniques can be applied. For example, a pattern formation method using a resist composition containing a compound represented by chemical formula (II) includes a step of coating a substrate with the resist composition containing the compound represented by chemical formula (II) directly or indirectly to form a resist film (coating step), a step of exposing the resist film formed by the coating step with active energy rays (exposure step), and a step of developing the exposed resist film using a developer to form a resist pattern (development step).

[0170] [Coating Process] A resist composition containing the compound represented by chemical formula (II) is applied to a substrate for integrated circuit manufacturing (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective coatings, etc.) or a substrate for mask circuit manufacturing (Cr, CrO, CrON, MoSi2, SiO2, etc.) by an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor coating, so that the coating film thickness is 0.01 to 2 μm. This is then pre-baked on a hot plate, preferably at 60 to 150°C for 10 seconds to 30 minutes, more preferably at 80 to 120°C for 30 seconds to 20 minutes, to form a resist film.

[0171] [Synthesis process] The resist film formed in the coating process is exposed using an active energy beam. Examples of active energy rays include ultraviolet light, far ultraviolet light, EB, EUV with wavelengths of 3-15 nm, X-rays, soft X-rays, excimer laser light, gamma rays, and synchrotron radiation. When using ultraviolet light, far ultraviolet light, EUV, X-rays, soft X-rays, excimer laser light, gamma rays, synchrotron radiation, etc. as the active energy ray, the exposure amount is preferably 1 to 200 mJ / cm², either directly or using a mask to form the desired pattern. 2 To the extent, more preferably 10 to 100 mJ / cm² 2 Irradiate to achieve the desired level of intensity. When using EB as the active energy beam, the exposure dose is preferably 0.1 to 1000 μC / cm². 2To a degree, more preferably 0.5 to 200 μC / cm² 2 Draw either directly or using a mask to form the desired pattern. Suitable active energy rays for fine patterning include i-rays with a wavelength of 365 nm, KrF excimer laser light, ArF excimer laser light, EB, EUV, X-rays, soft X-rays, gamma rays, and synchrotron radiation, with EB and EUV being more suitable for fine patterning.

[0172] After exposure with active energy rays, post-exposure baking (PEB) may be performed on a hot plate or in an oven, preferably at 50-150°C for 10 seconds to 30 minutes, more preferably at 60-120°C for 30 seconds to 20 minutes.

[0173] [Development process] After exposure or PEB, the exposed resist film is developed using an alkaline aqueous solution or organic solvent developer for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes, by conventional methods such as the dip method, puddle method, or spray method, thereby forming the desired pattern. In the case of a positive-type resist composition, the parts irradiated with light dissolve in the developer, while the parts that are not exposed do not dissolve, forming the desired positive-type pattern on the substrate. In the case of negative-type resist compositions, the opposite occurs compared to positive-type resist materials: the areas exposed to light become insoluble in the developer, while the areas not exposed dissolve.

[0174] Examples of alkaline aqueous developer solutions include 0.1 to 10% by mass, preferably 2 to 5% by mass, of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), etc. Examples of organic solvents used as developers include 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotate, ethyl crotate, Examples include methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenyl acetate, and 2-phenylethyl acetate. These developers may be used individually or mixed together.

[0175] At the end of the developing process, rinsing is performed. Examples of solvents used for rinsing include water, alcohols with 3 to 10 carbon atoms, ether compounds with 8 to 12 carbon atoms, alkanes, alkenes, alkynes, and aromatic solvents with 6 to 12 carbon atoms. Rinsing can reduce the occurrence of deformation and defects in the resist pattern. However, rinsing is not always necessary, and omitting it can reduce the amount of solvent used.

[0176] The developed hole patterns and trench patterns can also be shrunk using thermal flow, RELACS, or DSA techniques. A shrinking agent is applied to the hole pattern, and crosslinking of the shrinking agent occurs on the surface of the resist film due to the diffusion of an acid catalyst from the resist film during baking, causing the shrinking agent to adhere to the side walls of the hole pattern. The baking temperature is preferably 70 to 180°C, more preferably 80 to 170°C, and the baking time is preferably 10 to 300 seconds, during which excess shrinking agent is removed and the hole pattern is reduced in size. [Examples]

[0177] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The main raw materials used in the examples and comparative examples are as follows:

[0178] [Main raw materials] • 2,3,4,6-Tetraiodobenzoic acid: Synthesized according to the method described in Austrian Patent No. 209897. (See Chemical Formula (III-2).) • Benzyltrimethylammonium 2-hydroxy-1,1-difluoroethane-1-sulfonate: Synthesized according to the method described in Japanese Patent Publication No. 2011-16746. (See chemical formula (IV-1).) • N,N'-Diisopropylcarbodiimide: Manufactured by Fujifilm Wako Pure Chemical Industries. • Dimethylaminopyridine: Manufactured by Fujifilm Wako Pure Chemical Industries. • Dimethylaminopyridine hydrochloride: Synthesized according to the method described in Org. Lett., 2014, 16, 236-239. (See chemical formula (V-3).) • Benzyltrimethylammonium chloride: Manufactured by Tokyo Chemical Industry Co., Ltd. Triphenylsulfonium chloride: Manufactured by Tokyo Chemical Industry Co., Ltd. (See chemical formula (VII-1-1).)

[0179] [Example 1] <Synthesis of 4-dimethylaminopyridinium 2-(2,3,4,6-tetraiodobenzoyloxy)-1,1-difluoroethane-1-sulfonate (compound represented by chemical formula (I-2-5))> In a 300 ml three-necked round-bottom flask, 6.26 g (10.0 mmol) of 2,3,4,6-tetraiodobenzoic acid, 200.00 g of chloroform, 0.12 g (1.0 mmol) of dimethylaminopyridine, 2.52 g (20.0 mmol) of N,N'-diisopropylcarbodiimide, and 6.23 g (20.0 mmol) of benzyltrimethylammonium 2-hydroxy-1,1-difluoroethane-1-sulfonate were charged, and the mixture was stirred at 60°C for 24 hours. After cooling to 25°C, the precipitated crystals were filtered, and the resulting filtrate was subjected to three liquid-liquid extractions with 100.00 g of 5% aqueous solution of dimethylaminopyridine hydrochloride. Subsequently, the solvent was replaced with tetrahydrofuran, and the precipitated crystals were filtered to obtain 0.62 g of white crystals (yield: 7%).

[0180] This white crystal 1 H-NMR spectral data, 19 The F-NMR spectral data was as follows: · 1 H-NMR (d6-DMSO) δ: 8.41(s, 1H), 8.21(d, 2H), 6.98(d, 2H), 4.68(t, 2H), 3.19(s, 6H). · 19 F-NMR (d6-DMSO) δ: -118.6(t, 2F). Based on these spectral data, the obtained white crystals were identified as the compound indicated by the chemical formula (I-2-5). Furthermore, since no peaks other than those of the compound indicated by the title were detected in these spectral data, the purity of the compound indicated by the title was 100%.

[0181] [Example 2] <Synthesis of triphenylsulfonium 2-(2,3,4,6-tetraiodobenzoyloxy)-1,1-difluoroethane-1-sulfonate (compound represented by chemical formula (II-1-3))> In a 300 ml three-necked round-bottom flask, 8.92 g (10.0 mmol) of 4-dimethylaminopyridinium 2-(2,3,4,6-tetraiodobenzoyloxy)-1,1-difluoroethane-1-sulfonate, 200.00 g of chloroform, 50.00 g of deionized water, and 4.48 g (15.0 mmol) of triphenylsulfonium chloride were charged, and the mixture was stirred at 30°C for 24 hours. The organic layer was then obtained by liquid-liquid separation. The obtained organic layer was washed with 50.00 g of deionized water, concentrated, and 50.00 g of heptane was added dropwise. After addition, the precipitated crystals were filtered to obtain 6.07 g of white crystals (yield: 67%).

[0182] This white crystal 1 H-NMR spectral data, 19 The F-NMR spectral data was as follows: · 1 H-NMR (d6-DMSO) δ: 8.40 (s, 1H), 7.88-7.75(m, 15H), 4.66(t, 2H). · 19 F-NMR (d6-DMSO) δ: -115.10 (t, 2F) Based on these spectral data, the obtained white crystals were identified as the compound indicated by the chemical formula (II-1-3). Furthermore, since no peaks other than those of the compound indicated by the title were detected in these spectral data, the purity of the compound indicated by the title was 100%.

[0183] [Comparative Example 1] <Synthesis of benzyltrimethylammonium 2-(2,3,4,6-tetraiodobenzoyloxy)-1,1-difluoroethane-1-sulfonate (compound represented by chemical formula (X))> In a 300 ml three-necked round-bottom flask, 6.26 g (10.0 mmol) of 2,3,4,6-tetraiodobenzoic acid, 200.00 g of chloroform, 0.12 g (1.0 mmol) of dimethylaminopyridine, 2.52 g (20.0 mmol) of N,N'-diisopropylcarbodiimide, and 6.23 g (20.0 mmol) of benzyltrimethylammonium 2-hydroxy-1,1-difluoroethane-1-sulfonate were charged and stirred at 60°C for 24 hours. After cooling to 25°C, the precipitated crystals were filtered, and the resulting filtrate was subjected to three liquid-liquid extractions with 100.00 g of 5% aqueous solution of benzyltrimethylammonium chloride. Subsequently, the solvent was replaced with tetrahydrofuran, but no crystals formed. Therefore, the solution was concentrated under reduced pressure to obtain 7.90 g of a yellow viscous substance.

[0184] This yellow viscous substance 1 H-NMR spectral data, 19 The F-NMR spectral data was as follows: · 1 H-NMR (d6-DMSO) δ: 8.41(s, 1H), 8.36(s, 6.9H), 7.60-7.46(m, 5H), 5.48(d, 8.6H), 4.68(t, 2H), 4.51(s, 2H), 3.64(sep, 8.6H), 3.02(s, 9H), 1.00(d, 51.6H). · 19 F-NMR (d6-DMSO) δ: -118.6(t, 2F). These spectral data include peaks other than the compound mentioned in the title ( 1 The 1H-NMR spectrum included 8.36 (s, 6.9H), 5.48 (d, 8.6H), 3.64 (sep, 8.6H), and 1.00 (d, 51.6H). 1 Based on the integral ratio of the 1H-NMR spectrum (the integral ratio between the peak of the compound in the title and the peaks of other compounds), the purity of the compound in the title was determined to be 8%.

[0185] [ka]

[0186] [Comparative Example 2] <Synthesis of triphenylsulfonium 2-(2,3,4,6-tetraiodobenzoyloxy)-1,1-difluoroethane-1-sulfonate (compound represented by chemical formula (II-1-3))> In a 300 ml three-necked round-bottom flask, 8.92 g of the yellow viscous substance obtained in Comparative Example 1, 200.00 g of chloroform, 50.00 g of deionized water, and 4.48 g (15.0 mmol) of triphenylsulfonium chloride were charged, and the mixture was stirred at 30°C for 24 hours. After that, the reaction solution was... 1 H-NMR spectral data, 19 Upon reviewing the F-NMR spectral data, no peak was detected for the compound mentioned in the title.

[0187] [Example 3 and Comparative Example 3] Preparation of resist composition The resist compositions (Example 3 and Comparative Example 3) were prepared by mixing the following main ingredients in the proportions shown in Table 1 to obtain a homogeneous solution, and then filtering it through a membrane filter with a pore size of 0.2 μm.

[0188] [Main raw materials] (A) Polymers having structural units containing acid-reactive groups • Copolymer of 4-hydroxystyrene and 1-ethylcyclopentyl methacrylate: Synthesized in accordance with the method described in Japanese Patent Publication No. 2021-196578. (Hereinafter referred to as "polymer 1.") (B) Photoacid generator • Triphenylsulfonium 2-(2,3,4,6-tetraiodobenzoyloxy)-1,1-difluoroethane-1-sulfonate: Compound from Example 2 (PAG1) • Triphenylsulfonium 2-(2,3,5-triiodobenzoyloxy)-1,1-difluoroethane-1-sulfonate: Synthesized according to the method described in International Publication No. 2022 / 265034. (See chemical formula (XI). Hereafter, it may be referred to as "PAG2".)

[0189] [ka]

[0190] (C) Acid diffusion control agent • Triphenylsulfonium salicylate: Synthesized according to the method described in International Publication No. 2015 / 019983. (Hereinafter referred to as "PDB1".) (D) Solvent • Propylene glycol monomethyl ether acetate: Manufactured by Kanto Chemical Co., Ltd. (hereinafter sometimes referred to as "PGMEA"). • γ-Butyrolactone: Manufactured by Kanto Chemical Co., Ltd. (hereinafter sometimes referred to as "GBL").

[0191] [Test Example 1] Evaluation of Sensitivity The sensitivity of the resist compositions (Example 3 and Comparative Example 3) was evaluated as follows. (1) A resist composition was applied to a 2 cm square silicon substrate using a spin coater, and a 50 nm thick resist film was formed by performing a pre-bake (PAB) treatment on a hot plate at 110°C for 90 seconds. (2) Using an electron beam lithography system (ELS-7500EX manufactured by Elionix Corporation), the exposure amount was changed in steps on the formed resist film to create a line and space pattern (half pitch 100 nm) after development. (3) The substrate after exposure was subjected to post-exposure heating (PEB) treatment at 110°C for 90 seconds. (4) The substrate after PEB treatment was subjected to alkaline development at 25°C for 60 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (NMD-3, manufactured by Tokyo Ohka Kogyo). (5) After alkaline development, the substrate was washed with pure water for 15 seconds to obtain a substrate (test piece) on which a resist pattern was formed. (6) The resist patterns of the obtained test specimens were observed using a scanning electron microscope (Hitachi High-Technologies Corporation "S-4800") to determine the exposure amount required to obtain a line-and-space pattern with a half-pitch of 100 nm. A lower exposure amount indicates higher sensitivity.

[0192] The results of the sensitivity evaluation are shown in Table 1.

[0193] [Table 1]

[0194] The resist composition of Example 3 containing PAG1 formed a resist pattern with less exposure compared to the resist composition of Comparative Example 3 containing PAG2. This indicates that PAG1 is more sensitive to active energy rays than PAG2. [Industrial applicability]

[0195] The compound represented by chemical formula (I) of the present invention can be purified to high purity because it contains a pyridinium cation having an amino group. Therefore, the compound of the present invention is useful as an intermediate for photoacid generators. Furthermore, the photoacid generator produced from the compound of the present invention is useful, for example, as a photoacid generator for resists (especially chemically amplified resists) and as a photocationic polymerization initiator.

Claims

1. A compound represented by chemical formula (I). 【Chemistry 1】 (In the formula, R １ is a hydrogen atom or -CF ３ Represents R ２ and R ３ R represents the same or different hydrogen atom or an alkyl group having 1 to 5 carbon atoms, or ２ R ３ They may be linked together to form the rings shown in equations (a) to (f). (X represents an iodine atom.) 【Chemistry 2】

2. The compound according to claim 1, represented by chemical formula (Ia). 【Transformation 3】 (In the formula, R １ (This is the same as described above.)

3. A method for producing the compound according to claim 1, comprising the step of reacting tetraiodobenzoic acid represented by chemical formula (III) with a compound represented by chemical formula (IV), and then reacting it with a salt compound represented by chemical formula (V). 【Chemistry 4】 (wherein, R １ ~R ３ and X are the same as described above. [X ａ represents a halide ion.)

4. A method for producing a compound represented by chemical formula (II), comprising the step of reacting the compound described in claim 1 with a compound represented by chemical formula (VII). 【Transformation 5】 (In the formula, R １ ~R ３ And X are as described above. n represents an integer between 1 and 2. [A] ｎ＋ [X] represents an n-valent countercation. ｂ ] are halide ions, hydroxide ions, and trifluoromethanesulfonate (TfO － ), methanesulfonate (MsO － ), toluene sulfonate (TsO － (This refers to benzenesulfonate, benzoate, methoxide, ethoxide, t-butoxide, nitrite ion, or nitrate ion.)

5. [A] ｎ＋ The manufacturing method according to claim 4, wherein the countercation is a monovalent countercation represented by formulas (1) to (3). 【Transformation 6】 (In the formula, R １ａ ~R １ｃ , R ２ａ ~R ２ｃ These are the same or different halogen atoms, -CF ３ , -SO ２ R ５ , -SF ５ ----CHR １１ CH ２ X １ , alkyl groups having 1 to 10 carbon atoms, -OR １１ , -COOH, -NO ２ R represents a polymerizable group or an acid-reactive group. ３ａ and R ３ｂ These are the same or different halogen atoms, -CF ３ , -SO ２ R ６ , -SF ５ ----CHR １１ CH ２ X １ , alkyl groups having 1 to 10 carbon atoms, -OR １１ , -COOH, -NO ２ R represents a polymerizable group or an acid-reactive group. ５ -CF ３ , -CF ２ CF ３ R represents an alkyl group having 1 to 10 carbon atoms, or a phenyl group. ６ R represents an alkyl group having 1 to 10 carbon atoms, or a phenyl group. １１ X represents a hydrogen atom or a methyl group. １ represents a halogen atom, a mesyloxy group (OMs), a tosyloxy group (OTs), or a trifluoromethanesulfonyloxy group (OTf). １ It is a single bond, -O-, -S-, -S(O)- or -S(O) ２ It represents a negative value. m1 to m3 represent integers from 0 to 5. p1 represents an integer from 0 to 5. p2 and p3 represent integers from 0 to 4. q1 and q2 represent integers from 0 to 5. When m1 is an integer between 2 and 5, multiple R １ａ They may be the same or different, and when m2 is an integer from 2 to 5, multiple R １ｂ They may be the same or different, and when m3 is an integer from 2 to 5, multiple R １ｃ They may be the same or different. When p1 is an integer from 2 to 5, multiple R ２ａ They may be the same or different, and when p2 is an integer from 2 to 4, multiple R ２ｂ They may be the same or different, and when p3 is an integer between 2 and 4, multiple R ２ｃ They may be the same or different. When q1 is an integer from 2 to 5, multiple R ３ａ They may be the same or different, and when q2 is an integer from 2 to 5, multiple R ３ｂ They may be the same or different.

6. A photoacid generator characterized by containing a compound produced by the manufacturing method described in claim 4 or 5.

7. A compound represented by chemical formula (II). 【Transformation 7】 (In the formula, R １ is a hydrogen atom or -CF ３ This represents an iodine atom. X represents an iodine atom. n represents an integer between 1 and 2. [A] ｎ＋ (This represents an n-valent countercation.)

8. [A] ｎ＋ The compound according to claim 7, wherein the compound is a monovalent countercation represented by formulas (1) to (3). 【Transformation 8】 (wherein, R １ａ to R １ｃ , R ２ａ to R ２ｃ are the same or different and represent a halogen atom, -CF ３ , -SO ２ R ５ , -SF ５ , -CHR １１ CH ２ X １ , an alkyl group having 1 to 10 carbon atoms, -OR １１ , -COOH, -NO ２ , a polymerizable group, or an acid-reactive group. R ３ａ and R ３ｂ are the same or different and represent a halogen atom, -CF ３ , -SO ２ R ６ , -SF ５ , -CHR １１ CH ２ X １ , an alkyl group having 1 to 10 carbon atoms, -OR １１ , -COOH, -NO ２ , a polymerizable group, or an acid-reactive group. R ５ represents -CF ３ , -CF ２ CF ３ , an alkyl group having 1 to 10 carbon atoms, or a phenyl group. R ６ represents an alkyl group having 1 to 10 carbon atoms, or a phenyl group. R １１ represents a hydrogen atom or a methyl group, and X １ represents a halogen atom, a mesyloxy group (OMs), a tosyloxy group (OTs), or a trifluoromethanesulfonyloxy group (OTf). Y １ represents a single bond, -O-, -S-, -S(O)- or -S(O) ２ -. m1 to m3 represent integers from 0 to 5. p1 represents an integer from 0 to 5. p2 and p3 represent integers from 0 to 4. q1 and q2 represent integers from 0 to 5. When m1 is an integer from 2 to 5, the plurality of Rs １ａ may be the same or different, and when m2 is an integer from 2 to 5, the plurality of Rs １ｂ may be the same or different, and when m3 is an integer from 2 to 5, the plurality of Rs １ｃ may be the same or different. When p1 is an integer from 2 to 5, the plurality of Rs ２ａ may be the same or different, and when p2 is an integer from 2 to 4, the plurality of Rs ２ｂ may be the same or different, and when p3 is an integer from 2 to 4, the plurality of Rs ２ｃ may be the same or different. When q1 is an integer from 2 to 5, the plurality of Rs ３ａ may be the same or different, and when q2 is an integer from 2 to 5, the plurality of Rs ３ｂ may be the same or different. )

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