Resist composition and method for producing resist pattern

Abstract

To provide a resist composition and the like which allow a resist pattern having good LER to be produced.SOLUTION: The resist composition contains: an acid generator containing a salt represented by formula (I); and a resin containing a structural unit having an acid-labile group and a structural unit represented by formula (a2-A). [In the formula (I), R1-R5 each represent a halogen atom or a perfluoroalkyl group; R6-R8 each represent a halogen atom, a hydroxy group or the like; m5 represents an integer of 1-5; m6 and m7 represent integers of 0-3; m8 represents an integer of 0-4; and Q1 and Q2 each represent a fluorine atom or a perfluoroalkyl group.]SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a salt for an acid generator used in the fine processing of semiconductors, an acid generator containing the salt, and a resist The present invention relates to a resist composition and a method for producing a resist pattern. [Background technology]

[0002] Patent Document 1 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. The composition is described. TIFF0007624483000001.tif3366 [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2017-015777 A Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention provides a resist pattern having a better quality than a resist pattern formed from a resist composition containing the above salt. The present invention provides a salt capable of producing resist patterns with favorable line edge roughness (LER). The purpose is to provide [Means for solving the problem]

[0005] The present invention includes the following inventions. [1] A salt represented by formula (I). TIFF0007624483000002.tif4563 [In formula (I), R 1 , R 2 , R 3 , R 4 and R 5 each independently represents a halogen atom or a group having 1 to 6 carbon atoms represents a perfluoroalkyl group. R 6 , R 7 and R 8 each independently represents a halogen atom, a hydroxyl group, or a group having 1 to 6 carbon atoms or an alkyl group having 1 to 12 carbon atoms, CH2- may be replaced by -O- or -CO-. m5 represents an integer of 1 to 5, and when m5 is 2 or more, a plurality of R 5 are the same They may be the same or different. m6 represents an integer of 0 to 3, and when m6 is 2 or more, a plurality of R 6 are the same They may be the same or different. m7 represents an integer of 0 to 3, and when m7 is 2 or more, a plurality of R 7 are the same They may be the same or different. m8 represents an integer of 0 to 4, and when m8 is 2 or more, a plurality of R 8 are the same They may be the same or different, provided that 1≦m5+m8≦5. AI - represents an organic anion. [2] AI - However, sulfonate anion, sulfonylimide anion, sulfonylmethide The salt according to [1], which is an anion and a carboxylate anion. [3] AI - is a sulfonate anion, and the sulfonate anion is represented by the formula (IA): The salt according to [1] or [2], wherein the anion is TIFF0007624483000003.tif2352[In formula (IA), Q 1 and Q 2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms; It represents a aryl group. L 1represents a saturated hydrocarbon group having 1 to 24 carbon atoms, and the —CH 2- may be replaced by -O- or -CO-, and the water contained in the saturated hydrocarbon group The nitrogen atom may be substituted with a fluorine atom or a hydroxy group. Y 1 is a methyl group which may have a substituent or a substituted group having 3 to 4 carbon atoms 18 alicyclic hydrocarbon groups, and -CH2- contained in the alicyclic hydrocarbon groups is -O-, may be replaced by -SO2- or -CO-. [4] An acid generator comprising the salt according to any one of [1] to [3]. [5] A resist composition comprising the acid generator according to [4] and a resin having an acid labile group. [6] The structural unit having an acid labile group is a structural unit represented by formula (a1-1) and a structural unit represented by formula (a The resist composition according to [5], which contains at least two kinds of structural units represented by 1-2). TIFF0007624483000004.tif3985 [In formula (a1-1) and formula (a1-2), L a1 and L a2 are each independently -O- or *-O-(CH2) k1 -CO-O k1 represents an integer of 1 to 7, and * represents a bonding site with -CO-. R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, It represents an alicyclic hydrocarbon group or a combination thereof. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3. [7] The composition further contains a salt that generates an acid having a weaker acidity than the acid generated from the acid generator. 5] or [6]. A resist composition according to the above. [8] (1) A process for applying the resist composition according to any one of [5] to [7] onto a substrate. About (2) A step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) A method for producing a resist pattern, comprising the step of developing the composition layer after heating. Effect of the Invention

[0006] By using a resist composition using the salt of the present invention, it is possible to obtain good line edge roughness. A resist pattern can be produced using a laser elimination process (LER). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] In this specification, the term "(meth)acrylic monomer" refers to a monomer having a structure such as "CH2=CH-CO-" Monomers having the structure "CH2=C(CH3)-CO-" and monomers having the structure "CH2=C(CH3)-CO-" Similarly, "(meth)acrylate" and "(Meth)acrylic acid" refers to a compound selected from the group consisting of acrylate and methacrylate. "At least one selected from the group consisting of acrylic acid and methacrylic acid" and "at least one selected from the group consisting of acrylic acid and methacrylic acid "CH2=C(CH3)-CO-" or "CH2=CH-C When a structural unit having "O-" is exemplified, structural units having both groups are also included. In addition, in the groups described in this specification, straight chain structures and branched structures are For those which can have both structures, either one is acceptable. , including all stereoisomers. In this specification, the term "solid content of a resist composition" refers to the fraction of the total amount of the resist composition that is This refers to the total of all components excluding the solvent (E) described below.

[0008] <Salt represented by formula (I)> The present invention relates to a salt represented by formula (I) (hereinafter sometimes referred to as "salt (I)"). In salt (I), the side with a negative charge is called an anion (I) and the side with a positive charge is called a cationic salt (I). It is sometimes called "On(I)". R 1 , R 2 , R 3 , R 4 and R 5 The halogen atoms include fluorine, chlorine, and bromine. Examples of the atom include a hydrogen atom and an iodine atom. R 1 , R 2 , R 3 , R 4 and R 5 As the perfluoroalkyl group having 1 to 6 carbon atoms, Trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoro Isopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluoro Examples include a tert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. do. R 1 , R 2 , R 3 , R 4 and R 5 are each independently preferably a perylene having 1 to 3 carbon atoms. A fluoroalkyl group or a fluorine atom is preferable, and a trifluoromethyl group or a fluorine atom is more preferable. It is a fluorine atom, and more preferably a fluorine atom.

[0009] R 6 , R 7 and R 8Examples of the fluorinated alkyl group having 1 to 6 carbon atoms include trifluoromethyl. group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, perfluoropropyl group, 2,2,3,3, 3-Pentafluoropropyl group, perfluorobutyl group, 1,1,2,2,3,3,4, 4-Octafluorobutyl group, Perfluoropentyl group, 2,2,3,3,4,4,5, Examples of fluorinated alkyl groups include 5,5-nonafluoropentyl and perfluorohexyl groups. can be done. R 6 , R 7 and R 8 Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, and a propyl group. propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl The alkyl groups include, for example, hexyl, octyl, and nonyl groups. is preferably 1 to 9, and more preferably 1 to 4. R 6 , R 7 and R 8 The -CH2- contained in the alkyl group represented by the formula: When it is replaced with -, the number of carbon atoms before the replacement is regarded as the total number of carbon atoms of the alkyl group. T, R 6 , R 7 and R 8 The alkyl group represented by the formula: A group in which -CH2- is replaced by -O-), a carboxyl group (a -CH2 -CH2- is replaced with -O-CO-), an alkoxy group having 1 to 6 carbon atoms (a group having A group in which -CH2- in an alkyl group having 2 to 7 carbon atoms is replaced with -O- 7. Alkoxycarbonyl group (-CH2-CH2- contained in an alkyl group having 4 to 9 carbon atoms) is replaced by -O-CO-), alkylcarbonyl group having 2 to 7 carbon atoms (group having 3 carbon atoms A group in which -CH2- in an alkyl group having 2 to 8 carbon atoms is replaced with -CO- 7. Alkylcarbonyloxy group (-CH2-C contained in alkyl group having 4 to 9 carbon atoms) H2- may be replaced with -CO-O-. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and Examples of the aryloxy group include an oxy group, a pentyloxy group, and a hexyloxy group. Alkoxycarbonyl groups having 2 to 7 carbon atoms, alkylcarbonyl groups having 2 to 7 carbon atoms, and The alkylcarbonyloxy group having a carbon number of 2 to 7 is a group having a carbonyl group or an alkoxy group described above. It represents a group to which a carbonyl group or a carbonyloxy group is bonded. Examples of the alkoxycarbonyl group having 2 to 7 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, and A carbonyl group, a butoxycarbonyl group, etc., may be mentioned. An alkylcarbonyl group having 2 to 7 carbon atoms may be mentioned. Examples of the aryl group include an acetyl group, a propionyl group, and a butyryl group. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyloxy group, and the like. Examples of such an alkyl group include an aryloxy group. R 6 and R 7 are each independently preferably a fluorine atom, a hydroxyl group, or a group having 1 to 10 carbon atoms. 3 Fluorinated alkyl group or an alkyl group having 1 to 3 carbon atoms (-CH2 - may be replaced by -O- or -CO-, and more preferably is a fluorine atom. Preferably, the aryl group is a fluorine atom or a trifluoromethyl group, and more preferably, the aryl group is a fluorine atom. R 8 is preferably a fluorine atom, a hydroxyl group, a fluorinated alkyl group having 1 to 3 carbon atoms, or An alkyl group having 1 to 3 carbon atoms (wherein the -CH2- in the alkyl group is -O- or -CO- and more preferably a fluorine atom or a trifluoromethyl group. , a hydroxy group, a methyl group, a methoxy group or a methylcarbonyloxy group, and more preferably A fluorine atom is preferred. m6 and m7 are preferably 0 to 2, more preferably 0 or 1, and further preferably 0. m5 is preferably an integer of 1 to 3, and more preferably 1 or 2. m8 is preferably an integer of 0 to 2, more preferably 0 or 1. In addition, 1≦m It is preferable that 5+m8≦4, and it is more preferable that 1≦m5+m8≦3.

[0010] Examples of the cation (I) include the following cations: TIFF0007624483000005.tif44143

[0011] TIFF0007624483000006.tif139147

[0012] AI - Examples of the organic anion represented by the formula (I) include a sulfonate anion, a sulfonylimide anion, Examples of the anion include the AI ​​anion, the sulfonylmethide anion, and the carboxylate anion. - Represented by The organic anion is preferably a sulfonate anion, and is an anion represented by the formula (IA) It is more preferable that: TIFF0007624483000007.tif2965[In formula (IA), Q 1 and Q 2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms; It represents a aryl group. L 1 represents a saturated hydrocarbon group having 1 to 24 carbon atoms, and the —CH 2- may be replaced by -O- or -CO-, and the water contained in the saturated hydrocarbon group The nitrogen atom may be substituted with a fluorine atom or a hydroxy group. Y 1 is a methyl group which may have a substituent or a substituted group having 3 to 4 carbon atoms 18 alicyclic hydrocarbon groups, and -CH2- contained in the alicyclic hydrocarbon groups is -O-, may be replaced by -SO2- or -CO-.

[0013] In formula (IA), -CH2- contained in the saturated hydrocarbon group is -O- or -C(=O )-, the number of carbon atoms before the substitution is regarded as the number of carbon atoms of the saturated hydrocarbon group. In addition, -CH2- contained in the alicyclic hydrocarbon group is -O-, -SO2- or -C(=O). When it is replaced with -, the number of carbon atoms before the replacement is regarded as the number of carbon atoms of the alicyclic hydrocarbon group. .

[0014] Q 1 and Q 2 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms include trifluoromethyl. perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group , perfluoropentyl group, and perfluorohexyl group. Q 1 and Q 2 are each independently a fluorine atom or a trifluoromethyl group. It is preferable that both are fluorine atoms.

[0015] L 1 The divalent saturated hydrocarbon group in the formula (I) is a straight-chain alkanediyl group, a branched alkanediyl group, and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. A group formed by combining two or more of these may also be used. Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4 -diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 ,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1 ,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane- 1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17- Linear alkanediyl groups such as diyl groups; Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group branched alkanediyl groups such as 2-methylbutane-1,4-diyl group; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa Cycloalkanediyl groups such as cyclohexene-1,4-diyl group and cyclooctane-1,5-diyl group a monocyclic divalent alicyclic saturated hydrocarbon group, Norbornane-1,4-diyl group, Norbornane-2,5-diyl group, Adamantane- Polycyclic divalent alicyclic saturated carbons such as 1,5-diyl and adamantane-2,6-diyl groups Hydrogen groups and the like. L 1 The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula: The replaced group is, for example, a group represented by any one of formulas (b1-1) to (b1-3). The groups represented by formulae (b1-1) to (b1-3) and their specific examples are In the examples of the groups represented by formulae (b1-4) to (b1-11), * and ** represent bonding sites. represents the number of places, and * represents -Y 1 represents the binding site with

[0016] TIFF0007624483000008.tif26117[In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxy groups, and the saturated The --CH2-- contained in the hydrocarbon group may be replaced by --O-- or --CO--. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxy groups, and the saturated The --CH2-- contained in the hydrocarbon group may be replaced by --O-- or --CO--. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom or a hydroxy group. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxy groups, and the saturated The --CH2-- contained in the hydrocarbon group may be replaced by --O-- or --CO--. However, L b6 and L b7 The total number of carbon atoms is 23 or less.

[0017] In the groups represented by formulae (b1-1) to (b1-3), the saturated hydrocarbon group When -CH2- is replaced by -O- or -CO-, the number of carbon atoms before the replacement is The number of carbon atoms in the hydrocarbon group. As the divalent saturated hydrocarbon group, L b1 The divalent saturated hydrocarbon groups are the same as those mentioned above. can be. L b2 is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, The hydrogen atom contained in the hydrogen group may be substituted with a fluorine atom. L b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms. L b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. In the divalent saturated hydrocarbon group, -CH2- is replaced with -O- or -CO-. This is also fine. L 1 The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula: The replaced group is preferably a group represented by formula (b1-1) or formula (b1-3).

[0018] Examples of the formula (b1-1) include groups represented by the formulas (b1-4) to (b1-8). Can be obtained. TIFF0007624483000009.tif49119[In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom or a hydroxy group. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, The contained --CH2-- may be replaced by --O-- or --CO--. L b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. . However, L b9 and L b10 The total number of carbon atoms is 20 or less. In formula (b1-6), L b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. . However, L b11 and L b12 The total number of carbon atoms is 21 or less. In formula (b1-7), L b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. L b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The --CH2-- contained in the hydrocarbon group may be replaced by --O-- or --CO--. L b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. . However, L b13 ~L b15 The total number of carbon atoms is 19 or less. In formula (b1-8), L b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The -CH2- contained in the formula may be replaced by -O- or -CO-. L b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. L b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. . However, L b16 ~L b18 The total number of carbon atoms is 19 or less. L b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, more preferably More preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, more preferably More preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, more preferably More preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0019] The group represented by formula (b1-3) is represented by formulas (b1-9) to (b1-11), Examples of the groups include those represented by the following formula: TIFF0007624483000010.tif24140 formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by The atom may be substituted with a hydroxy group. However, L b19 and L b20 The total number of carbon atoms is 23 or less. In formula (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by The atom may be substituted with a hydroxy group. However, L b21 , L b22 and L b23 The total number of carbon atoms is 21 or less. In formula (b1-11), L b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by The atom may be substituted with a hydroxy group. However, L b24 , L b25 and L b26 The total number of carbon atoms is 21 or less. In addition, in the groups represented by formulae (b1-9) to (b1-11), When a hydrogen atom in a hydrocarbon group is substituted with an alkylcarbonyloxy group, The number of carbon atoms before substitution is regarded as the number of carbon atoms of the saturated hydrocarbon group. The alkylcarbonyloxy group includes an acetyloxy group, a propionyloxy group, a bromooxy group, Thyryloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group etc.

[0020] Examples of the group represented by formula (b1-4) include the following. TIFF0007624483000011.tif17153

[0021] Examples of the group represented by formula (b1-5) include the following. TIFF0007624483000012.tif79161

[0022] Examples of the group represented by formula (b1-6) include the following. TIFF0007624483000013.tif53149

[0023] Examples of the group represented by formula (b1-7) include the following. TIFF0007624483000014.tif62153

[0024] Examples of the group represented by formula (b1-8) include the following. TIFF0007624483000015.tif24151

[0025] Examples of the group represented by formula (b1-2) include the following. TIFF0007624483000016.tif30162

[0026] Examples of the group represented by formula (b1-9) include the following. TIFF0007624483000017.tif45136

[0027] Examples of the group represented by formula (b1-10) include the following. TIFF0007624483000018.tif94165

[0028] Examples of the group represented by formula (b1-11) include the following. TIFF0007624483000019.tif85163

[0029] Y 1 Examples of the alicyclic hydrocarbon group represented by the formula (Y1) to the formula (Y11) and the formula (Y36) -A group represented by the formula (Y38) is exemplified. Y 1 The -CH2- contained in the alicyclic hydrocarbon group represented by the formula: When it is replaced by -CO-, the number of the groups may be one or more. Examples of the groups include those represented by formulae (Y12) to (Y35) and (Y39) to (Y41). * is L 1 represents the binding site with TIFF0007624483000020.tif85165

[0030] Y 1 The alicyclic hydrocarbon group represented by the formula (Y1) to the formula (Y20), the formula (Y26), Formula (Y27), Formula (Y30), Formula (Y31), Formula (Y39) ~ Formula (Y41) and more preferably, a group represented by formula (Y11), formula (Y15), or formula (Y1 6), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula ( Y39) or (Y40), and more preferably a group represented by formula (Y11), formula (Y 15), a group represented by formula (Y20), formula (Y30), formula (Y39) or formula (Y40). do. Y 1 is a spiro ring represented by the formula (Y28) to the formula (Y35), etc. In this case, the alkanediyl group between the two oxygen atoms preferably has one or more fluorine atoms. In addition, among the alkanediyl groups contained in the ketal structure, the methyl group adjacent to the oxygen atom is preferably The ethylene group is preferably not substituted with a fluorine atom.

[0031] Y 1 The substituent of the methyl group represented by the formula (I) is a halogen atom, a hydroxyl group, a methyl group having 3 to 4 carbon atoms, 16 alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, glycidyloxy groups, - (CH2) ja -CO-OR b1 Group or -(CH2) ja -O-CO-R b1 group (in the formula , R b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a represents an aromatic hydrocarbon group having a number of 6 to 18 or a combination thereof; It represents any one of the following integers: an alkyl group having 1 to 16 carbon atoms, and an alicyclic hydrocarbon group having 3 to 16 carbon atoms. The -CH2- in the radical is replaced by -O-, -S(O)2- or -CO-. (etc.) Y1 The substituent of the alicyclic hydrocarbon group represented by the formula (I) is a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms which may be substituted with a hydroxy group; an alicyclic group having 3 to 16 carbon atoms; Formula hydrocarbon groups, alkoxy groups having 1 to 12 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, Aralkyl groups with prime numbers of 7 to 21, alkylcarbonyl groups with carbon numbers of 2 to 4, glycidyloxy Group, -(CH2) ja -CO-OR b1 Group or -(CH2) ja -O-CO-R b1 base (In the formula, R b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or a combination thereof; 4. An alkyl group having 1 to 16 carbon atoms and an alicyclic group having 3 to 16 carbon atoms. The -CH2- in the hydrocarbon group is replaced by -O-, -S(O)2- or -CO-. ) and the like.

[0032] Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms. do. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, and a cyclohexyl group. butyl group, cyclooctyl group, norbornyl group, adamantyl group, etc. The hydrocarbon group may have a chain hydrocarbon group, and examples thereof include a methylcyclohexyl group, a dimethyl Examples thereof include a cyclohexyl group. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and the like. Examples of the aromatic hydrocarbon group include aryl groups such as an alkyl group and an aryl group such as a phenyl group and a phenanthryl group. It may have a hydrocarbon group or an alicyclic hydrocarbon group, and may have a chain hydrocarbon group having 1 to 18 carbon atoms. Aromatic hydrocarbon groups (tolyl, xylyl, cumenyl, mesityl, p-methyl Phenyl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethyl phenyl group, 2-methyl-6-ethylphenyl group, etc.), and alicyclic carbons having 3 to 18 carbon atoms. Aromatic hydrocarbon groups having a hydride group (p-cyclohexylphenyl group, p-adamantyl phenyl group, etc. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a bromoalkyl group. butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group , 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group etc. Examples of alkyl groups substituted with hydroxy groups include hydroxymethyl groups, hydroxy Examples of such groups include hydroxyalkyl groups such as an ethyl group. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, aryloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy groups. The aralkyl group includes a benzyl group, a phenethyl group, a phenylpropyl group, a naphthyl group, and the like. Examples of the alkyl group include ethyl and naphthylethyl groups. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. etc.

[0033] Y 1 Examples include the following: TIFF0007624483000021.tif125144

[0034] TIFF0007624483000022.tif81127

[0035] Y 1 is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. More preferably, it is an alicyclic hydrocarbon group substituted with a hydroxy group, and even more preferably, an adamantyl group which may have a substituent, In the formula, -CH2- may be replaced by -CO-, -S(O)2- or -CO-. Yes. Y 1 is more preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, mantyl group or the group represented by the following formula, and particularly preferably a hydroxyadamantyl group or is an oxoadamantyl group, and groups containing these. TIFF0007624483000023.tif94151

[0036] The anion represented by formula (IA) is represented by formulas (IA-1) to (IA-55). The anion represented by the formula (hereinafter, it may be referred to as "anion (IA-1)" depending on the formula number) Formula (IA-1) to Formula (IA-4), Formula (IA-9), Formula (I- A-10), formula (IA-24) to formula (IA-33), formula (IA-36) to formula (I- A-40), an anion represented by any one of formulas (IA-47) to (IA-55) More preferred. TIFF0007624483000024.tif79142

[0037] TIFF0007624483000025.tif96153

[0038] TIFF0007624483000026.tif62157

[0039] TIFF0007624483000027.tif64147

[0040] TIFF0007624483000028.tif185157

[0041] TIFF0007624483000029.tif113162

[0042] Here, R i2 ~R i7 are each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably R is a methyl group or an ethyl group. i8 is, for example, a chain hydrocarbon having 1 to 12 carbon atoms. a group, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or More preferably, the group formed by combining these is a methyl group, an ethyl group, or a cyclohexyl group. It is a silyl group or an adamantyl group. A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q is a 1 and Q 2 has the same meaning as above. Specific examples of the anion represented by formula (IA) include those described in JP 2010-204646 A. Examples of the anions include those described in Gazette No.

[0043] The anion represented by formula (IA) is preferably an anion represented by formula (Ia-1) to formula (Ia- 34) are examples of anions represented by the following formulas: TIFF0007624483000030.tif89155

[0044] TIFF0007624483000031.tif140142

[0045] TIFF0007624483000032.tif83168

[0046] TIFF0007624483000033.tif79153

[0047] Among them, the compounds represented by formula (Ia-1) to formula (Ia-3) and the compounds represented by formula (Ia-7) to formula (Ia- 19), and anions represented by any one of formulas (Ia-22) to (Ia-34) are preferred. It is nice.

[0048] AI - Examples of the sulfonylimide anion represented by the formula (I) include the following. TIFF0007624483000034.tif41130

[0049] Examples of sulfonylmethide anions include the following: TIFF0007624483000035.tif30128

[0050] Examples of carboxylate anions include the following: TIFF0007624483000036.tif51154

[0051] Specific examples of the salt (I) include salts of any combination of the above-mentioned cations and anions. Specific examples of the salt (I) are shown in the table below. In the table below, each symbol represents the symbol attached to the structure representing the above-mentioned anion or cation. For example, salt (I-1) is a compound having an anion represented by formula (Ia-1) and an anion represented by formula (Ic-1) and a cation represented by the formula: TIFF0007624483000037.tif3987

[0052] [Table 1] TIFF0007624483000039.tif223154 TIFF0007624483000040.tif223154 TIFF0007624483000041.tif223154 TIFF0007624483000042.tif88155

[0053] Among them, salt (I) is salt (I-1) to salt (I-5), salt (I-13) to salt (I-25) , salt (I-30) ~ salt (I-34), salt (I-42) ~ salt (I-54), salt (I-59) ~Salt (I-63), Salt (I-71) ~Salt (I-83), Salt (I-88) ~Salt (I-92) , Salt(I-100)~Salt(I-112), Salt(I-117)~Salt(I-121), Salt(I -129) to salt (I-141).

[0054] <Method for producing salt (I)> The salt (I) can be prepared by dissolving a salt represented by formula (Ia) and a salt represented by formula (Ib) in a solvent. It can be produced by reacting TIFF0007624483000043.tif60157 [wherein all symbols have the same meanings as defined above.] Solvents include chloroform, monochlorobenzene, acetonitrile, water, etc. can be. The reaction temperature is usually 15° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0055] Examples of the salt represented by formula (Ib) include salts represented by the following formulas: can be obtained by a method similar to that described in JP 2011-116747 A. JPEG0007624483000044.jpg79134

[0056] The salt of formula (Ia) is a compound of formula (Ic) and a compound of formula (Ib) and magnesium (Id) in a solvent to obtain a Grignard compound. The compound was reacted in a solvent in the presence of trimethylchlorosilane and a base, and then further reacted with dimethylsilane. It can be prepared by reacting with ethyl sulphuric acid. JPEG0007624483000045.jpg68144 [wherein all symbols have the same meanings as defined above.] The solvent may be tetrahydrofuran or the like. The base includes triethylamine and the like. The reaction temperature is usually 5° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0057] Examples of the compound represented by formula (Ic) include compounds represented by the following formula: The compound represented by (Ic) can be prepared by the method described in JP 2017-015777 A. It can be obtained by the method of TIFF0007624483000046.tif2741

[0058] Compounds represented by formula (Id) include the following compounds, which are commercially available: It is easily available. TIFF0007624483000047.tif26139

[0059] <Acid generator> The acid generator of the present invention is an acid generator containing a salt (I). Alternatively, two or more types of salt (I) may be contained. In addition to the salt (I), the acid generator of the present invention may be an acid generator known in the resist field (hereinafter, “acid generator”). The acid generator (B) may be used alone. Alternatively, two or more of them may be used in combination.

[0060] The acid generator (B) may be either a nonionic or ionic acid generator. Biocides include sulfonate esters (e.g., 2-nitrobenzyl esters, aromatic sulfonates, etc.). sulfonates, oximesulfonates, N-sulfonyloxyimides, sulfonyloxyketones ton, diazonaphthoquinone 4-sulfonate), sulfones (e.g. disulfone, ketone Examples of ionic acid generators include oni Onium salts containing ion cations (e.g. diazonium salts, phosphonium salts, sulfonium salts) The anion of the onium salt is typically a sulfonate anion. ion, sulfonylimide anion, sulfonylmethide anion, etc.

[0061] Examples of the acid generator (B) include those described in JP-A-63-26653 and JP-A-55-164824. JP-A-62-69263, JP-A-63-146038, JP-A-63-163452 , JP-A-62-153853, JP-A-63-146029, U.S. Pat. No. 3,779, 778, U.S. Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. Compounds that generate an acid when exposed to radiation, such as those described in US Pat. No. 5,312,712, can be used. In addition, a compound produced by a known method may be used. The acid generator (B) may be a compound containing two or more kinds of compounds. They may also be used in combination.

[0062] The acid generator (B) is preferably a fluorine-containing acid generator, more preferably represented by the formula (B1): (hereinafter, may be referred to as "acid generator (B1)"). TIFF0007624483000048.tif2862[In formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents an alkyl group. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, The -CH2- may be replaced by -O- or -CO-, and the saturated hydrocarbon group The hydrogen atoms contained therein may be substituted with fluorine atoms or hydroxy groups. Y is a methyl group which may have a substituent or a substituted group having 3 to 1 carbon atoms. 8, and -CH2- contained in the alicyclic hydrocarbon group is -O-, - It may be replaced by S(O)2- or -CO-. Z1 + represents an organic cation.

[0063] Q in formula (B1) b1 , Q b2 , L b1 and Y are each represented by the above formula (IA). Q in 1 , Q 2 , L 1 and Y 1 And similar things can be mentioned. The sulfonate anion in formula (B1) may be an anion represented by formula (IA) Similar examples include:

[0064] Z1 + Examples of the organic cation include organic onium cations, organic sulfonium cations, Organic iodonium cations, organic ammonium cations, benzothiazolium cations and Among these, organic sulfonium cations are Preferred are iodonium and organic iodonium cations, and more preferred are arylsulfonium cations. Specifically, the cation represented by any one of formulas (b2-1) to (b2-4) (hereinafter Below, depending on the formula number, it may be called "cation (b2-1)" etc.)

[0065] TIFF0007624483000049.tif77115In equations (b2-1) to (b2-4), R b4 ~R b6 each independently represents a chain hydrocarbon group having 1 to 30 carbon atoms, It represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and the chain hydrocarbon group The hydrogen atoms contained in the alkyl group are hydroxyl groups, alkoxy groups having 1 to 12 carbon atoms, and fatty acids having 3 to 12 carbon atoms. The alicyclic group may be substituted with a cyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atoms contained in the hydrocarbon group are halogen atoms, aliphatic hydrocarbon groups having 1 to 18 carbon atoms, may be substituted with an alkylcarbonyl group having 2 to 4 carbon atoms or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group is replaced by a halogen atom, a hydroxyl group, or a C1 It may be substituted with up to 12 alkoxy groups. R b4 and R b5 are bonded together to form a ring with the sulfur atom to which they are attached The -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. good. R b7 and R b8 each independently represents a hydroxyl group or an aliphatic hydrocarbon group having 1 to 12 carbon atoms; Or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer of 0 to 5. When m2 is 2 or more, multiple R b7 may be the same or different, and when n2 is 2 or more, R in Numbers b8 may be the same or different. R b9 and R b10 each independently represents a chain hydrocarbon group having 1 to 36 carbon atoms or a chain hydrocarbon group having 3 to 4 carbon atoms, Represents 36 alicyclic hydrocarbon groups. Rb9 and R b10 are bonded together to form a ring with the sulfur atom to which they are attached The -CH2- contained in the ring may be replaced with -O-, -S- or -CO-. Good too. R b11 is a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, It represents a hydrogen group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or It represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, and a hydrogen atom contained in the chain hydrocarbon is It may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the aromatic hydrocarbon group The hydrogen atom is preferably an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyl group having 1 to 12 carbon atoms. It may be substituted with an oxy group. R b11 and R b12 means that they are bonded together to form a ring including the -CH-CO- to which they are attached. The -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. It is also possible. R b13 ~R b18 each independently represents a hydroxyl group or an aliphatic hydrocarbon group having 1 to 12 carbon atoms; Or an alkoxy group having 1 to 12 carbon atoms. L b31 represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer of 0 to 5. q2 and r2 each independently represent an integer of 0 to 4. u2 represents 0 or 1. When o2 is 2 or more, multiple R b13 are the same or different, and when p2 is 2 or more, multiple R b14are the same or different, and when q2 is 2 or more, multiple R b15 are the same or different, r2 When is 2 or more, multiple R b16 are the same or different, and when s2 is 2 or more, multiple R b17 teeth Identical or different, when t2 is 2 or more, multiple R b18 are the same or different.

[0066] The aliphatic hydrocarbon group refers to a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and Examples of the alkyl group include a 2-ethylhexyl group. In particular, R b9 ~R b12 The chain hydrocarbon group preferably has 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the hydrogen group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. cycloalkyl groups such as cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl groups; Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, group, a norbornyl group, and the following groups. TIFF0007624483000050.tif10159 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably has 4 to 12 carbon atoms. Examples of alicyclic hydrocarbon groups in which hydrogen atoms are replaced by aliphatic hydrocarbon groups include methylcyclohexane. cyclohexyl, dimethylcyclohexyl, 2-methyladamantan-2-yl, 2-ethyl 2-Isopropyladamantan-2-yl group, methylnor Examples of the alkyl group include a bornyl group and an isobornyl group. In the alicyclic hydrocarbon group, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably Preferably, it is 20 or less.

[0067] Examples of the aromatic hydrocarbon group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, Examples of the aromatic hydrocarbon group include an aryl group such as a phenanthryl group. or an alicyclic hydrocarbon group, and an aromatic hydrocarbon group having a chain hydrocarbon group ( tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert -Butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group etc.) and aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc. The aromatic hydrocarbon group is a chain hydrocarbon group. In the case where an alicyclic hydrocarbon group is contained, it is preferably a chain hydrocarbon group having 1 to 18 carbon atoms and a chain hydrocarbon group having 3 to 4 carbon atoms. Alicyclic hydrocarbon groups of 18 are preferred. Examples of aromatic hydrocarbon groups in which hydrogen atoms are substituted with alkoxy groups include p-methoxyphenyl. Examples of the alkyl group include aryl groups. Examples of the chain hydrocarbon group in which a hydrogen atom is replaced by an aromatic hydrocarbon group include a benzyl group, a phenoxy group, and the like. ethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc. Examples thereof include aralkyl groups.

[0068] The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, aryloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy groups. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. can be done. Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms. do. The alkylcarbonyloxy group includes a methylcarbonyloxy group, an ethylcarbonyloxy group, and an ethyl Oxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group Si group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyl Examples thereof include an oxy group and a 2-ethylhexylcarbonyloxy group.

[0069] R b4 and R b5 and form a ring together with the sulfur atom to which they are attached: The ring may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated. The ring may be one having 3 to 18 carbon atoms, and preferably one having 4 to 18 carbon atoms. The ring containing a sulfur atom may be a 3- to 12-membered ring, preferably a 3- to 7-membered ring. Examples include the rings shown below, where * represents a binding site. TIFF0007624483000051.tif24142

[0070] R b9 and R b10 The ring formed by combining with may be monocyclic, polycyclic, aromatic or non-aromatic. The ring may be either a saturated or unsaturated ring. Examples of the ring include a 3-membered ring to a 12-membered ring. Preferably, it is a 3- to 7-membered ring. For example, a thiolane-1-ium ring (tetrahydrothio ophenium ring), thian-1-ium ring, 1,4-oxathiane-4-ium ring, etc. Can be obtained. R b11 and R b12 The ring formed by combining with may be monocyclic, polycyclic, aromatic or non-aromatic. The ring may be either a saturated or unsaturated ring. Examples of the ring include a 3-membered ring to a 12-membered ring. and preferably a 3- to 7-membered ring. Oxocycloheptane ring, oxocyclohexane ring , oxonorbornane ring, oxoadamantane ring, etc.

[0071] Among the cations (b2-1) to (b2-4), the cation (b2 -1). Examples of the cation (b2-1) include the following cations. TIFF0007624483000052.tif149157

[0072] Examples of the cation (b2-2) include the following cations. TIFF0007624483000053.tif17140

[0073] Examples of the cation (b2-3) include the following cations. TIFF0007624483000054.tif32155

[0074] Examples of the cation (b2-4) include the following cations. TIFF0007624483000055.tif140153

[0075] The acid generator (B) is a combination of the above-mentioned sulfonate anion and the above-mentioned organic cation. The acid generator (B) is preferably a compound represented by the formula (B1 Formulae (B1a-1) to (B1a-3) and Formulae (B1a-7) to (B1a-16), Formula (B1a- 18), (B1a-19), (B1a-22) to (B1a-34) and a combination of the anion (b2-1) or the cation (b2-3). can be.

[0076] The acid generator (B) is preferably one represented by formula (B1-1) to formula (B1-48), Among them, those containing an arylsulfonium cation are preferred. Formula (B1-1) ~ Formula (B1-3), Formula (B1-5) ~ Formula (B1-7), Formula (B1-11) ~Formula (B1-14), Formula (B1-20) ~Formula (B1-26), Formula (B1-29), Formula (B Those represented by formulas (B1-31) to (B1-48) are particularly preferred. TIFF0007624483000056.tif119149

[0077] TIFF0007624483000057.tif77147

[0078] TIFF0007624483000058.tif146146

[0079] TIFF0007624483000059.tif60155

[0080] TIFF0007624483000060.tif108142

[0081] In the case where the acid generator contains a salt (I) and an acid generator (B), the salt (I) and the acid generator (B) The ratio of the contents of the salt (I):acid generator (B) (mass ratio; salt (I):acid generator (B)) is usually 1:99 to 99:1. The ratio is preferably 2:98 to 98:2, and more preferably 5:95 to 95:5. , more preferably 10:90 to 90:10, and particularly preferably 15:85 to 85: It is 15.

[0082] <Resist Composition> The resist composition of the present invention comprises an acid generator containing a salt (I) and a resin having an acid labile group (hereinafter Here, the "acid labile group" refers to a group that is eliminated by When the structural unit is contacted with an acid, the leaving group is eliminated, and the structural unit becomes a hydrophilic group (e.g., a hydroxyl group). It means a group that converts into a structural unit having a silyl group or a carboxy group. The resist composition of the present invention generates an acid having a weaker acidity than the acid generated from the acid generator. It may contain a quencher such as a salt (hereinafter referred to as "quencher (C)"). It is preferable that the ink contains a solvent (hereinafter, sometimes referred to as "solvent (E)").

[0083] <Acid generator> In the resist composition of the present invention, the content of the acid generator is 100% by weight of the resin (A) described below. With respect to the amount of the glycerol, the amount is preferably 1 part by mass or more and 40 parts by mass or less, and more preferably 3 parts by mass or more and 30 parts by mass or less. It is 5 parts by mass or less, and more preferably 10 parts by mass or more and 35 parts by mass or less.

[0084] <Resin (A)> Resin (A) contains a structural unit having an acid labile group (hereinafter sometimes referred to as “structural unit (a1)”). The resin (A) may further contain a structural unit other than the structural unit (a1). As the structural unit other than the structural unit (a1), a structural unit not having an acid labile group ( (hereinafter sometimes referred to as "structural unit (s)"), structural unit (a1) and structural unit (s) other than (for example, a structural unit having a halogen atom described later (hereinafter referred to as "structural unit (a4) "), a structural unit having a non-leaving hydrocarbon group described below (hereinafter referred to as a "structural unit ( a5) and other structural units derived from monomers known in the art Examples include:

[0085] <Structural unit (a1)> The structural unit (a1) is a monomer having an acid labile group (hereinafter referred to as "monomer (a1)"). In some cases, The acid labile group contained in the resin (A) is a group represented by formula (1) (hereinafter, also referred to as group (1)). ) and / or a group represented by formula (2) (hereinafter also referred to as group (2)) is preferred. TIFF0007624483000061.tif1988 [In formula (1), R a1 , R a2 and R a3 Each independently represents an alkyl group having 1 to 8 carbon atoms. R represents a cyclic group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a combination thereof; a1 Reach BiR a2 are non-aromatic carbon atoms with 3 to 20 carbon atoms that bond together with the carbon atoms to which they are attached. It forms a hydrogen ring. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * denotes a binding site.] TIFF0007624483000062.tif2171[In formula (2), R a1’ and R a2’ each independently represents a hydrogen atom or a group having 1 to 1 carbon atoms R represents a hydrocarbon group of a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2’ Reach BiR a3’ are bonded to each other and, together with the carbon atom to which they are bonded and X, A heterocyclic ring is formed, and the -CH2- contained in the hydrocarbon group and the heterocyclic ring is -O- or -S- may be substituted. X represents an oxygen atom or a sulfur atom. na′ represents 0 or 1. * denotes a binding site.]

[0086] R a1 , R a2 and R a3 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, Examples of the alkyl group include an aryl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. R a1 , R a2 and R a3 The alicyclic hydrocarbon group in may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, Examples of cycloalkyl groups include cycloheptyl and cyclooctyl groups. Examples of the hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups: (* represents a bonding site). a1 , R a2 and R a3 Alicyclic carbonization of The hydrogen group preferably has 3 to 16 carbon atoms. TIFF0007624483000063.tif10150 Examples of the group combining an alkyl group and an alicyclic hydrocarbon group include methylcyclohexane. xyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group , adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc. do. Preferably, ma is 0 and na is 1. R a1 and R a2 When they are bonded to each other to form a non-aromatic hydrocarbon ring, -C(R a1 )(R a2 )(R a3 The non-aromatic hydrocarbon ring is preferably a carbon ring. The numbers are 3 to 12. * indicates the bonding site with -O-. TIFF0007624483000064.tif30139

[0087] R a1’ , R a2’ and R a3’ The hydrocarbon group in the Examples of the alkyl group include a fluorine atom, an aromatic hydrocarbon group, and a group formed by combining these groups. can be done. The alkyl group and the alicyclic hydrocarbon group are R a1 , R a2 and R a3 The same groups as those listed in The following are some of the reasons. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples of the aryl group include a phenanthryl group. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. (e.g., cycloalkylalkyl groups), aralkyl groups such as benzyl groups, and alkyl groups. Aromatic hydrocarbon groups (p-methylphenyl, p-tert-butylphenyl, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl- 6-ethylphenyl group, etc.), aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexyl p-adamantylphenyl group, p-adamantylphenyl group, phenylcyclohexyl group, etc. Examples include aryl-cycloalkyl groups. R a2’ and R a3’ are bonded to each other and together with the carbon atom to which they are bonded and X, When a ring is formed, -C(R a1’ )(R a3’ )-XR a2’ Examples of the ring include the following: * indicates the binding site. TIFF0007624483000065.tif19130R a1’ and R a2’At least one of these is preferably a hydrogen atom. na' is preferably 0.

[0088] Examples of the group (1) include the following groups. In formula (1), R a1 , R a2 and R a3 is an alkyl group, ma=0, and n A group where a=1. As the group, a tert-butoxycarbonyl group is preferable. In formula (1), R a1 , R a2 However, together with the carbon atoms to which they are bonded, they form adamantane. Forming a ethyl group, R a3 is an alkyl group, ma=0, and na=1. In formula (1), R a1 and R a2 are each independently an alkyl group; R a3 Adama A group in which ma=0 and na=1. Specific examples of the group (1) include the following groups: * represents a binding site. TIFF0007624483000066.tif95154

[0089] Specific examples of the group (2) include the following groups: * represents a bonding site. TIFF0007624483000067.tif76162

[0090] The monomer (a1) is preferably a monomer having an acid labile group and an ethylenically unsaturated bond. More preferably, it is a (meth)acrylic monomer having an acid labile group.

[0091] Of the (meth)acrylic monomers having an acid labile group, those having 5 to 20 carbon atoms are preferred. Examples of such a bulky structure include those having an alicyclic hydrocarbon group. A resin (A) having a structural unit derived from a monomer (a1) having the above structure is used in a resist composition. This can improve the resolution of the resist pattern.

[0092] As a structural unit derived from a (meth)acrylic monomer having a group (1), 0) (hereinafter, may be referred to as structural unit (a1-0)), -1) (hereinafter, may be referred to as structural unit (a1-1)) or a1-2) (hereinafter, may be referred to as structural unit (a1-2)). These may be used alone or in combination of two or more. The structural unit is (a1-1) and / or (a1-2). TIFF0007624483000068.tif39126 [In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 , L a1 and L a2 are each independently -O- or *-O-(CH2) k1 - represents CO-O-, k1 represents an integer of 1 to 7, and * represents the bonding site with -CO-. represent. R a01 , R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a02 , R a03 and R a04 each independently represents an alkyl group having 1 to 8 carbon atoms, 18 alicyclic hydrocarbon groups or combinations thereof. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, It represents an alicyclic hydrocarbon group or a group formed by combining these. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3.

[0093] R a01 , R a4 and R a5 is preferably a methyl group. L a01 , L a1 and L a2 is preferably an oxygen atom or *-O-(CH2) k01 -C OO- (wherein k01 is preferably an integer of 1 to 4, more preferably 1), and more preferably an oxygen atom. R a02 , R a03 , R a04 , R a6 and R a7 The alkyl group, alicyclic hydrocarbon group, and As a group combining these, R in group (1) a1 , R a2 and R a3 The same groups as those listed in Examples include: R a02 , R a03 , and R a04 The number of carbon atoms in the alkyl group is preferably 1 to 6. More preferably, it is a methyl group or an ethyl group, and even more preferably, it is a methyl group. R a6 and R a7 The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably Preferably, it is a methyl group, an ethyl group, or an isopropyl group, and more preferably, it is an ethyl group or an isopropyl group. It is a isopropyl group. R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms of the alicyclic hydrocarbon group is preferably It is 5 to 12, and more preferably 5 to 10. The group consisting of a combination of an alkyl group and an alicyclic hydrocarbon group is It is preferred that the total number of carbon atoms in combination with the group is 18 or less. R a02 and R a03 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably methyl It is a phenyl group or an ethyl group. R a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms. is preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. be. R a6 and R a7 are each independently preferably an alkyl group having 1 to 6 carbon atoms, More preferably, it is a methyl group, an ethyl group, or an isopropyl group, and even more preferably, it is an ethyl group. or an isopropyl group. m1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0094] Examples of the structural unit (a1-0) include those represented by the formulae (a1-0-1) to (a1-0-12): and R in the structural unit (a1-0) a01 The equivalent The structural units represented by the formula (a1-0-1) to the formula (a1- 0-10) are preferred. TIFF0007624483000069.tif65159

[0095] Examples of the structural unit (a1-1) include those described in JP-A-2010-204646. Among them, structural units derived from the monomers of formula (a1-1-1) to formula (a1-1-2) are included. -1-4) and R in the structural unit (a1-1) a4 In accordance with The structural units represented by the formulae (a1-1-1) to (a1-1-2) are preferably those in which the corresponding methyl groups are replaced by hydrogen atoms. A structural unit represented by any one of (a1-1-4) is more preferred. TIFF0007624483000070.tif43119

[0096] The structural unit (a1-2) is any one of the structural units represented by formula (a1-2-1) to (a1-2-6). The structural unit represented by the formula (a1-2) is R a5 The methyl group corresponding to The structural units are represented by the formula (a1-2-2), the formula (a1-2-5), and Formula (a1-2-6) is preferred. TIFF0007624483000071.tif35155

[0097] When the resin (A) contains the structural unit (a1-0), the content of the structural unit (a1-0) is determined based on the total amount of the structural units of the resin (A). The amount is usually 5 to 60 mol %, preferably 5 to 50 mol %, more preferably The content is usually 10 to 40 mol %. When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), The total content of these units is usually 10 to 95 mol % based on the total structural units of the resin (A). The content is preferably 15 to 90 mol %, more preferably 20 to 85 mol %, and further preferably Preferably, it is 25 to 80 mol %, and even more preferably, it is 30 to 75 mol %.

[0098] The structural unit (a1) having the group (2) is represented by the formula (a1-4). Examples of the structural unit include a structural unit (hereinafter sometimes referred to as "structural unit (a1-4)"). TIFF0007624483000072.tif4070[In formula (a1-4), R a32 is a hydrogen atom, a halogen atom, or a C1 group optionally having a halogen atom Represents an alkyl group of 1 to 6. R a33 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, Alkoxy groups, alkylcarbonyl groups having 2 to 4 carbon atoms, alkylcarbonyl groups having 2 to 4 carbon atoms It represents an acryloyloxy group, an acryloyloxy group, or a methacryloyloxy group. la represents an integer of 0 to 4. When la is 2 or more, a plurality of R a33 are mutual may be the same or different. R a34 and R a35 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R a36 are combined with each other and These form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -CO- to which they are bonded, and the hydrocarbon The -CH2- contained in the alkyl group and the divalent hydrocarbon group is replaced by -O- or -S-. That's fine.]

[0099] R a32 and R a33 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples of the alkyl group include propyl, butyl, pentyl and hexyl groups. An alkyl group having 1 to 4 carbon atoms is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is Even more preferred. R a32 and R a33Examples of the halogen atom in the formula (I) include a fluorine atom, a chlorine atom, and a bromine atom. Examples include: Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include trifluoromethyl. ethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, perfluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group 2,2,3,3,3-pentafluoropropyl, propyl, perfluoropropyl butyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoro 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, Examples of the alkyl group include an ethyl group, a hexyl group, and a perfluorohexyl group. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, Among them, alkoxy groups having 1 to 4 carbon atoms are particularly preferred. A methoxy group or an ethoxy group is preferred, and a methoxy group is even more preferred. . Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. can be. The alkylcarbonyloxy group includes an acetyloxy group, a propionyloxy group, a bromooxy group, Examples thereof include a thyloxy group. R a34 , R a35 and R a36 The hydrocarbon group in the formula (I) is an alkyl group or an alicyclic hydrocarbon group. , aromatic hydrocarbon groups, and groups combining these. The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a hexyl group. Examples include a silyl group, a heptyl group, and an octyl group. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the aryl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthalene, The following groups (* indicates a bonding site): Some examples include: TIFF0007624483000073.tif10151 Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, biphenyl, Examples of the aryl group include a phenanthryl group. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. (e.g., cycloalkylalkyl groups), aralkyl groups such as benzyl groups, and alkyl groups. Aromatic hydrocarbon groups (p-methylphenyl, p-tert-butylphenyl, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl- 6-ethylphenyl group, etc.), aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexyl p-adamantylphenyl group, p-adamantylphenyl group, phenylcyclohexyl group, etc. In particular, R a36 As for the carbon number 1-18, an alkyl group, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or Examples of the groups include groups formed by combining these.

[0100] In formula (a1-4), R a32 is preferably a hydrogen atom. R a33 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group. is more preferred, and a methoxy group is even more preferred. la is preferably 0 or 1, and more preferably 0. Ra34 is preferably a hydrogen atom. R a35 is preferably an alkyl group or an alicyclic hydrocarbon group having 1 to 12 carbon atoms, more preferably More preferably, it is a methyl group or an ethyl group. R a36 The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, Alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, or combinations thereof More preferably, it is an alkyl group having 1 to 18 carbon atoms, a group having 3 to 1 R is an alicyclic aliphatic hydrocarbon group having 8 or an aralkyl group having 7 to 18 carbon atoms. a36 In The alkyl group and the alicyclic hydrocarbon group are preferably unsubstituted. a36 Fragrance in The aromatic hydrocarbon group is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms. -OC(R a34 )(R a35 )-OR a36 is an acid (e.g. p-toluenesulfonic acid) and is eliminated to form a hydroxyl group.

[0101] Examples of the structural unit (a1-4) include those described in JP-A-2010-204646. The structural units derived from the monomers represented by the formula (a1-4-1) to (a1-4-2) are preferably included. -4-12) and R in the structural unit (a1-4) a32 To A structural unit in which the corresponding hydrogen atom is replaced by a methyl group is preferred. a1-4-1) to (a1-4-5) and (a1-4-10) are structural units represented by the formulas Rankings include: TIFF0007624483000074.tif70157

[0102] When the resin (A) contains the structural unit (a1-4), the content of the structural unit (a1-4) is determined based on the total structure of the resin (A). It is preferably 10 to 95 mol %, more preferably 15 to 90 mol %, based on the total of the units. More preferably, the content is 20 to 85 mol %, and even more preferably, the content is 20 to 70 mol %. It is even more preferable that the content is 20 to 60 mol %, and particularly preferable that the content is 20 to 60 mol %.

[0103] The structural unit derived from a (meth)acrylic monomer having the group (2) is represented by the formula (a1 -5) (hereinafter sometimes referred to as "structural unit (a1-5)") can also be mentioned. can be. TIFF0007624483000075.tif4658 formula (a1-5), R a8 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. Represents an halogen atom. Z a1 is a single bond or -(CH2) h3 -CO-L 54 -, h3 is 1 to 4 represents an integer, and * represents L 51 It represents the binding site with L 51 , L 52 , L 53 and L 54 each independently represents -O- or -S-. s1 represents an integer of 1 to 3. s1' represents an integer of 0 to 3.

[0104] Examples of the halogen atom include a fluorine atom and a chlorine atom, with a fluorine atom being preferred. Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, and an ethyl group. group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluoro group Examples of such groups include trifluoromethyl and trifluoromethyl groups. In formula (a1-5), R a8 is a hydrogen atom, a methyl group, or a trifluoromethyl group. preferable. L 51 is preferably an oxygen atom. L 52 and L 53 Of these, it is preferred that one is -O- and the other is -S-. It is preferable that s1 is 1. s1' is preferably an integer of 0 to 2. Z a1 is preferably a single bond or --CH2--CO--O--.

[0105] Examples of the structural unit (a1-5) include those described in JP-A-2010-61117. Among them, structural units derived from the monomers represented by the formula (a1-5-1) to the formula (a1-5- 4), and the structural units represented by the formula (a1-5-1) or the formula (a1-5-2) are preferred. ) is more preferred. TIFF0007624483000076.tif33133

[0106] When the resin (A) contains the structural unit (a1-5), the content of the structural unit (a1-5) is determined based on the total structure of the resin (A). The amount of the aryl group is preferably 1 to 50 mol %, more preferably 3 to 45 mol %, and more preferably 5 to 40 mol %. % by mole is more preferable, and 5 to 30 mol % is even more preferable.

[0107] Further, examples of the structural unit (a1) include the following structural units. TIFF0007624483000077.tif31162

[0108] When the resin (A) contains structural units such as those of (a1-3-1) to (a1-3-7) The content of the aryl group is preferably 10 to 95 mol % based on the total structural units of the resin (A), and more preferably 15 to 95 mol %. More preferably, the content is from 20 to 85 mol %, and even more preferably, the content is from 20 to 70 mol %. It is even more preferable, and particularly preferable is 20 to 60 mol %.

[0109] Structural unit(s) The structural unit (s) is a monomer that does not have an acid labile group (hereinafter referred to as "monomer (s)"). The monomer from which the structural unit (s) is derived is an acid-inhibiting monomer known in the resist field. Monomers that do not have stabilizing groups can be used. The structural unit (s) preferably has a hydroxy group or a lactone ring. A structural unit having an oxy group and no acid labile group (hereinafter referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and no acid labile group (hereinafter referred to as "structural unit" When a resin having the structural unit (a3) ​​is used in the resist composition of the present invention, For example, the resolution of the resist pattern and the adhesion to the substrate can be improved.

[0110] <Structural unit (a2)> The hydroxy group of the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. It may also be a carboxylic hydroxy group. When a resist pattern is produced from the resist composition of the present invention, the exposure light source is KrF Using high energy rays such as excimer laser (248 nm), electron beam or EUV (extreme ultraviolet light) In this case, the structural unit (a2) is a structural unit having a phenolic hydroxy group ( a2) is preferably used. In addition, ArF excimer laser (193 nm) or the like is used. In this case, the structural unit (a2) may be a structural unit (a2) having an alcoholic hydroxyl group. ) is preferred, and the structural unit (a2-1) described below is more preferred. As a2), one type may be contained alone, or two or more types may be contained.

[0111] The structural unit (a2) having a phenolic hydroxy group is represented by the formula (a2 -A) (hereinafter sometimes referred to as "structural unit (a2-A)"). can be. TIFF0007624483000078.tif4349[In formula (a2-A), R a50 is a hydrogen atom, a halogen atom, or a group having 1 to 6 carbon atoms which may have a halogen atom represents an alkyl group represented by the formula: R a51 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, Alkoxy groups, alkylcarbonyl groups having 2 to 4 carbon atoms, alkylcarbonyl groups having 2 to 4 carbon atoms It represents an acryloyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or *-X a51 -(A a52 -X a52 ) nb - stands for -R. a50 Combined represents the bonding site with the carbon atom. A a52 each independently represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O-, or -O-CO-. nb represents 0 or 1. mb represents an integer of 0 to 4. When mb is an integer of 2 or more, R in Numbers a51 may be the same or different.]

[0112] R a50 Examples of the halogen atom in the formula (I) include a fluorine atom, a chlorine atom, and a bromine atom. can be. R a50 As the alkyl group having 1 to 6 carbon atoms which may have a halogen atom, Trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2 ,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, phenyl 2,2,3,3,3-pentafluoropropyl group, propyl group, Perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoro Examples of the alkyl group include pentyl, pentyl, hexyl and perfluorohexyl groups. R a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group or is more preferably an ethyl group, and further preferably a hydrogen atom or a methyl group. R a51 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples of the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group are listed below. can be done. R a51 The alkoxy group in the formula (I) is a methoxy group, an ethoxy group, a propoxy group, an iso Examples of the group include a propoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. An alkoxy group having 1 to 4 carbon atoms is preferred, a methoxy group or an ethoxy group is more preferred, and a methoxy group or an ethoxy group is more preferred. A toxyl group is more preferred. R a51 The alkylcarbonyl group in the formula (I) is an acetyl group, a propionyl group, or a butyl group. Examples of the alkyl group include an aryl group. R a51 The alkylcarbonyloxy group in the formula (I) is an acetyloxy group, a propionyloxy group, Examples of the alkyl groups include an alkyloxy group and a butyryloxy group. R a51 is preferably a methyl group.

[0113] *-X a51 -(A a52 -X a52 ) nb - includes *-O-, *-CO-O-, *-OC O-, *-CO-OA a52 -CO-O-, *-O-CO-A a52 -O-, *-OA a52 -CO-O-, *-CO-OA a52 -O-CO-, *-O-CO-A a52 -O-CO-, Among them, *-CO-O- and *-CO-OA are the most common. a52 -CO-O- or *- Office Automation a52 -CO-O- is preferred.

[0114] Examples of the alkanediyl group include a methylene group, an ethylene group, and a propane-1,3-diyl group. Propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group , hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1, 3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and and 2-methylbutane-1,4-diyl group. A a52 is preferably a methylene group or an ethylene group.

[0115] A a50 is a single bond, *-CO-O- or *-CO-OA a52 -CO-O- Preferably, it is a single bond, *-CO-O- or *-CO-O-CH2-CO-O-. A single bond or *--CO--O-- is more preferable, and a single bond or *--CO--O-- is even more preferable.

[0116] mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0. The hydroxy group is preferably bonded to the o-position or p-position of the benzene ring, and more preferably to the p-position. More preferably, they are combined.

[0117] Examples of the structural unit (a2-A) include those described in JP-A-2010-204634 and JP-A-2012- Examples of structural units include those derived from monomers described in US Pat. No. 5,12577.

[0118] The structural unit (a2-A) is represented by the formulas (a2-2-1) to (a2-2-6). In the structural units and the structural units represented by formulae (a2-2-1) to (a2-2-6), R in structural unit (a2-A) a50 The structure in which the methyl group corresponding to is replaced by a hydrogen atom The structural unit (a2-A) is a structural unit represented by the formula (a2-2-1): A structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6) and a structural unit represented by formula (a2-2-7) A structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), or a structural unit represented by formula ( In the structural unit represented by a2-2-6), R in the structural unit (a2-A) a50 To It is preferable that the corresponding methyl group is substituted with a hydrogen atom. TIFF0007624483000079.tif42166

[0119] Content of structural unit (a2-A) when structural unit (a2-A) is contained in resin (A) is preferably 5 to 80 mol %, more preferably 10 to 70 mol %, based on all structural units. % by mole, more preferably 15 to 65 mol %, and even more preferably 20 to 65 mol %. It is 65 mol%. The structural unit (a2-A) can be prepared, for example, by polymerization of the structural unit (a1-4) followed by p-toluenesulfonyl chloride. It can be incorporated into the resin (A) by treating it with an acid such as benzenesulfonic acid. After polymerization using acetoxystyrene, etc., tetramethylammonium hydroxide, etc. By treating the resin with an alkali, the structural unit (a2-A) can be incorporated into the resin (A). can.

[0120] In the structural unit (a2), the structural unit having an alcoholic hydroxy group is represented by the formula ( a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)") Some examples include: TIFF0007624483000080.tif3954 formula (a2-1), L a3 is -O- or *-O-(CH2) k2 represents -CO-O-, k2 represents an integer of 1 to 7. * represents a bonding site with -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 each independently represents a hydrogen atom, a methyl group, or a hydroxy group. o1 represents an integer of 0 to 10.

[0121] In formula (a2-1), L a3 is preferably -O-, -O-(CH2) f1 -CO-O- (wherein f1 represents an integer of 1 to 4), and more preferably —O—. R a14 is preferably a methyl group. R a15 is preferably a hydrogen atom. R a16 is preferably a hydrogen atom or a hydroxy group. o1 is preferably an integer of 0 to 3, and more preferably 0 or 1.

[0122] Examples of the structural unit (a2-1) include those described in JP-A-2010-204646. The structural units derived from the monomers of formula (a2-1-1) to formula (a2-1-6) are included. ), and the structural unit represented by any one of the formulas (a2-1-1) to (a2-1-4) is preferred. A structural unit represented by any one of the formulas (a2-1-1) or (a2-1- The structural unit represented by 3) is more preferred. TIFF0007624483000081.tif49138

[0123] When the resin (A) contains the structural unit (a2-1), the content of the structural unit (a2-1) is determined based on the total amount of the structural units of the resin (A). The amount is usually 1 to 45 mol %, preferably 1 to 40 mol %, more preferably The content is preferably 1 to 35 mol %, and more preferably 2 to 20 mol %.

[0124] <Structural unit (a3)> The lactone ring contained in the structural unit (a3) ​​is a β-propiolactone ring, a γ-butyrolactone ring, or It may be a monocyclic ring such as a lactone ring or a δ-valerolactone ring, or a condensation ring of a monocyclic lactone ring with another ring. It may be a γ-butyrolactone ring, an adamantane lactone ring, or a γ -Bridged ring containing a butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)) Examples include:

[0125] The structural unit (a3) ​​is preferably represented by the formula (a3-1), the formula (a3-2), the formula (a3-3), or a structural unit represented by formula (a3-4). One of these may be contained alone, Two or more types may be contained. TIFF0007624483000082.tif45149 [In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4), L a4 , L a5 and L a6 are each independently -O- or *-O-(CH2) k3 - It represents a group represented by CO-O- (k3 represents an integer of any of 1 to 7). L a7 , -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -CO-OL a9 -CO-O- or *-OL a8 -O-CO-L a9 -O- vinegar. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * indicates the bonding site with the carbonyl group. R a18 , R a19 and R a20 each independently represents a hydrogen atom or a methyl group. R a24 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or represents a halogen atom. X a3 represents -CH2- or an oxygen atom. R a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R a22 , R a23 and R a25 each independently represents a carboxy group, a cyano group, or a carbon atom; Represents an aliphatic hydrocarbon group having 1 to 4 prime numbers. p1 represents an integer of 0 to 5. q1 represents an integer of 0 to 3. r1 represents an integer of 0 to 3. w1 represents an integer of 0 to 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a2 3 and / or R a25 may be the same or different.]

[0126] R a21 , R a22 , R a23 and R a25 The aliphatic hydrocarbon group in propyl, isopropyl, butyl, sec-butyl and tert-butyl groups Examples of alkyl groups include the following. R a24 The halogen atom in the formula (I) is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Examples of atoms include: R a24 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group, etc. Of these, preferred is an alkyl group having 1 to 4 carbon atoms, and more preferred is a methyl group. or an ethyl group. R a24 Examples of the alkyl group having a halogen atom in the formula (I) include a trifluoromethyl group, Perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group Examples of the alkyl group include an alkyl group, a triiodomethyl group, and a triiodomethyl group.

[0127] L a8 and L a9The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a proline group, Pan-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pe hexane-1,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-Methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentamethylpropane Examples include 2-methylbutane-1,4-diyl group and 2-methylbutane-1,4-diyl group.

[0128] In formulas (a3-1) to (a3-3), L a4 ~L a6 are each independently preferred or -O- or *-O-(CH2) k3 In -CO-O-, k3 is 1 to 4 More preferably, -O- and *-O-CH2-CO-O- are also preferred. An oxygen atom is preferred. R a18 ~R a21 is preferably a methyl group. R a22 and R a23 are each independently preferably a carboxy group, a cyano group or a methyl group. It is a ethyl group. p1, q1 and r1 each independently represent an integer of preferably 0 to 2; More preferably, it is 0 or 1.

[0129] In formula (a3-4), R a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably It is a hydrogen atom or a methyl group. R a25 is preferably a carboxy group, a cyano group or a methyl group. L a7 is preferably -O- or *-OL a8-CO-O-, more preferably -O-, -O-CH2-CO-O- or -O-C2H4-CO-O-. w1 is preferably an integer of 0 to 2, and more preferably 0 or 1. In particular, the formula (a3-4) is preferably the formula (a3-4)'. TIFF0007624483000083.tif4326 (in the formula, R a24 , L a7 has the same meaning as above.)

[0130] As the structural unit (a3), a monomer described in JP-A-2010-204646 can be used. , Monomers described in JP 2000-122294 A, and JP 2012-41274 A Examples of the structural unit (a3) ​​include structural units derived from the monomers described in the above publication. , formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula (a3-2-2) , Formula (a3-3-1), Formula (a3-3-2) and Formula (a3-4-1) to Formula (a3-4-1 2), and in the structural unit, the structural unit represented by any one of the formulas (a3-1) to (a3-2) R in a3-4) a18 , R a19 , R a20 and R a24 The methyl group corresponding to Atom-substituted structural units are preferred.

[0131] TIFF0007624483000084.tif115165

[0132] When the resin (A) contains the structural unit (a3), the total content of the structural unit (a3) ​​is the total content of all structural units of the resin (A). The amount is usually 5 to 70 mol %, preferably 10 to 65 mol %, more preferably Or, it is 10 to 60 mol %. In addition, the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit The content of the units (a3-4) is 5 to 60 moles per total structural units of the resin (A). % by mole, more preferably 5 to 50 mol %, and further preferably 10 to 50 mol %.

[0133] <Structural unit (a4)> Examples of the structural unit (a4) include the following structural units. TIFF0007624483000085.tif2553[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having 1 to 24 carbon atoms and containing a halogen atom, The -CH2- contained in the radical may be replaced by -O- or -CO. R 42 The saturated hydrocarbon group represented by the formula (I) is a chain saturated hydrocarbon group and a monocyclic or polycyclic alicyclic saturated Examples of the alkyl group include hydrocarbon groups and groups formed by combining these groups.

[0134] Examples of the chain saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, heptyl group, Examples include xadecyl, heptadecyl and octadecyl groups. Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include a cyclopentyl group and a cyclohexyl group. cycloalkyl groups such as cycloheptyl and cyclooctyl groups; decahydronaphthyl groups, Polycyclic alicyclic groups such as adamantyl group, norbornyl group, and the following groups (* indicates a bonding site): Examples include cyclic saturated hydrocarbon groups. TIFF0007624483000086.tif10146 The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an aryl group with one or more alicyclic saturated hydrocarbon groups. Examples of the saturated alicyclic hydrocarbon group include -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl Examples of the alkyl group include an aryl group, an alkanediyl group, an alicyclic saturated hydrocarbon group, and an alkyl group.

[0135] The structural unit (a4) may be a structural unit represented by formula (a4-0), a structural unit represented by formula (a4-1), and the structural unit represented by formula (a4-4). TIFF0007624483000087.tif3844[In formula (a4-0), R 54 represents a hydrogen atom or a methyl group. L 4a represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3a is a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluoroalkanediyl group having 3 to 12 carbon atoms. represents a fluorocycloalkanediyl group. R 64 represents a hydrogen atom or a fluorine atom.

[0136] L 4a The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a propane-1, linear alkanediyl groups such as butane-1,4-diyl group, ethane-1,1 -diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane Branched alkanes such as pan-1,3-diyl and 2-methylpropane-1,2-diyl groups An example of such a group is a diyl group.

[0137] L 3a The perfluoroalkanediyl group in the formula (I) is a difluoromethylene group, Fluoroethylene group, perfluoroethylfluoromethylene group, perfluoropropane- 1,3-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane- 2,2-diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2, 2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5 -diyl group, perfluoropentane-2,2-diyl group, perfluoropentane-3,3 -diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2 -diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7 -diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4 -diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8 -diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3,3 -diyl group, perfluorooctane-4,4-diyl group, and the like. L 3a The perfluorocycloalkanediyl group in xanediyl group, perfluorocyclopentanediyl group, perfluorocycloheptanediyl group yl group, perfluoroadamantanediyl group, and the like.

[0138] L 4a is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond, a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, more preferably or a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0139] The structural unit (a4-0) may be any of the structural units shown below and the structural units ( a4-0) in R 54The structural unit in which the methyl group corresponding to the can be. TIFF0007624483000088.tif93165

[0140] TIFF0007624483000089.tif4866[In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, The --CH2-- contained in the hydrocarbon group may be replaced by --O-- or --CO--. A a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent, or a group represented by the formula (ag 1), where A a41 and R a42 At least one of the The group has a halogen atom (preferably a fluorine atom). TIFF0007624483000090.tif1488 [In formula (a-g1), s represents 0 or 1. A a42 and A a44 each independently represents a divalent alkyl group having 1 to 5 carbon atoms which may have a substituent. Represents a saturated hydrocarbon group. A a43 represents a single bond or a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. Represents. X a41 and X a42 each independently represents -O-, -CO-, -CO-O-, or -O-CO - represents. However, A a42 , A a43 , A a44 , X a41 and X a42 The total number of carbon atoms is 7 or less. * indicates the binding site, and the * on the right is -O-CO-R a42This is the binding site for

[0141] R a42 The saturated hydrocarbon group in the formula (I) is preferably a chain saturated hydrocarbon group or a monocyclic or polycyclic saturated Alicyclic hydrocarbon groups, and groups formed by combining these groups, etc. do.

[0142] Examples of the chain saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, heptyl group, Examples of the alkyl group include a xadecyl group, a heptadecyl group, and an octadecyl group. Examples of the monocyclic or polycyclic saturated alicyclic hydrocarbon group include a cyclopentyl group and a cyclohexyl group. cycloalkyl groups such as cycloheptyl and cyclooctyl groups; decahydronaphthyl groups, Polycyclic alicyclic groups such as adamantyl group, norbornyl group, and the following groups (* indicates a bonding site): Examples of the cyclic hydrocarbon groups include cyclic hydrocarbon groups. TIFF0007624483000091.tif11159 The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more saturated alicyclic hydrocarbon groups. Examples of the alkyl groups include -alkanediyl group-saturated alicyclic hydrocarbon group, -saturated alicyclic hydrocarbon group-alkyl Examples of the alkyl group include an alkyl group, -alkanediyl group-saturated alicyclic hydrocarbon group-alkyl group, and the like.

[0143] R a42 The substituents which may be contained in the formula (a-g3) include a halogen atom and a The halogen atom may be at least one selected from the group consisting of fluorine, arylene ... Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable. TIFF0007624483000092.tif855[In formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O- (* represents R a42 ) which represents the binding site with A a45 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. * denotes a binding site.] However, R a42 -X a43 -A a45 In R a42 If A does not have a halogen atom, a4 5 represents a saturated hydrocarbon group having 1 to 17 carbon atoms and at least one halogen atom.

[0144] A a45 The saturated hydrocarbon group in the formula (I) is a methyl group, an ethyl group, a propyl group, or a butyl group. , pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecayl group, Alkyl groups such as cyclohexyl, hexadecyl, heptadecyl and octadecyl groups; monocyclic alicyclic groups such as butyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; Hydrocarbon groups; as well as decahydronaphthyl groups, adamantyl groups, norbornyl groups, and the following and polycyclic and alicyclic hydrocarbon groups such as the group (* represents a bonding site). TIFF0007624483000093.tif11157 The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more alicyclic hydrocarbon groups. In particular, -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group Examples thereof include a candiyl group-alicyclic hydrocarbon group-alkyl group.

[0145] R a42 is preferably a saturated hydrocarbon group which may have a halogen atom, and / or a saturated hydrocarbon group having a group represented by formula (a-g3) is preferably This is more preferable. R a42 When is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom. More preferably, it is a saturated hydrocarbon group having a fluoroalkyl group or a perfluorosilyl group. Preferably, the alkyl group is a chloroalkyl group, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms. Particularly preferred is a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a perfluoromethyl group, a perfluoroethyl group, and a perfluoropropyl group. , perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoro perfluorooctyl and perfluoroheptyl groups. Examples of the aryl group include a perfluorocyclohexyl group. R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), g3), including the number of carbon atoms contained in the group represented by R a42 The total number of carbon atoms is preferably 15 or less. When the alkyl group has a group represented by formula (a-g3) as a substituent, The number is preferably one.

[0146] R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), R a42 Yes, More preferably, it is a group represented by formula (a-g2). TIFF0007624483000094.tif871[In formula (a-g2), A a46represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. represent. X a44 represents *-O-CO- or *-CO-O- (* represents A a46 It represents the binding site with ). A a47 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. However, A a46 , A a47 and X a44 The total number of carbon atoms in A is 18 or less. a46 and A a47 of At least one of them has at least one halogen atom. * indicates the bonding site with the carbonyl group.]

[0147] A a46 The saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms. A a47 The saturated hydrocarbon group preferably has 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms. a 47 is more preferably a cyclohexyl group or an adamantyl group.

[0148] A preferred structure of the group represented by formula (a-g2) is the following structure (* represents a carbonyl group). (This is the binding site for TIFF0007624483000095.tif3194

[0149] A a41 The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a propane-1, 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 linear alkanediyl groups such as propane-1,2-diyl, butane-1,6-diyl; ,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4- and branched alkanediyl groups such as 2-methylbutane-1,4-diyl and the like. do. A a41 The substituents in the alkanediyl group represented by the formula (I) are a hydroxy group and an alkanediyl group having 1 to 10 carbon atoms. Examples of the alkoxy group include alkoxy groups represented by the formula (6). A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably It is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.

[0150] A in the group represented by formula (a-g1) a42 , A a43 and A a44 The bivalent saturation represented by The saturated hydrocarbon group includes linear or branched alkanediyl groups and monocyclic divalent alicyclic saturated carbon groups. By combining a fluorine atom with an alkanediyl group and a divalent saturated alicyclic hydrocarbon group, Specifically, a methylene group, an ethylene group, a divalent saturated hydrocarbon group formed by propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group yl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group group, and 2-methylpropane-1,2-diyl group. A a42 , A a43 and A a44 The substituent of the divalent saturated hydrocarbon group represented by is hydroxyl. Examples of the alkoxy group include an alkoxy group and an alkoxy group having 1 to 6 carbon atoms. It is preferred that s is 0.

[0151] In the group represented by formula (a-g1), X a42 is -O-, -CO-, -CO-O- or Examples of the -O-CO- group include the following groups. In the following examples, * and ** indicates each binding site, and ** is -O-CO-R a42 This is the binding site for TIFF0007624483000096.tif46140

[0152] The structural unit represented by formula (a4-1) includes the structural units shown below and the structural units shown below. R in the structural unit represented by formula (a4-1) a41 A methyl group corresponding to Examples of structural units that have been replaced include: TIFF0007624483000097.tif91136

[0153] TIFF0007624483000098.tif132151

[0154] The structural unit represented by formula (a4-1) includes a structural unit represented by formula (a4-2) and Examples of the structural unit include those represented by formula (a4-3). TIFF0007624483000099.tif4156[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 represents an alkanediyl group having 1 to 6 carbon atoms, H2- may be replaced by -O- or -CO-. R f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms and containing a fluorine atom. However, L 44 and R f6 The total number of carbon atoms in the molecule is limited to 21.

[0155] L 44 The alkanediyl group having 1 to 6 carbon atoms is represented by A a41 The same groups as those exemplified in can be. R f6 The saturated hydrocarbon group of R 42 Examples of the groups include the same groups as those exemplified in the above. L 44 The alkanediyl group in the formula (I) is preferably an alkanediyl group having 2 to 4 carbon atoms. An ethylene group is more preferred.

[0156] Examples of the structural unit represented by formula (a4-2) include the structural units represented by formulae (a4-1-1) to (a4 -1-11) are structural units represented by the following formulas. R f5 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-2). It can be mentioned as a structural unit.

[0157] TIFF0007624483000100.tif5671[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 represents an alkanediyl group having 1 to 6 carbon atoms. A f13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom. vinegar. X f12 represents *-O-CO- or *-CO-O- (* represents A f13 represents the binding site with ). A f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may contain a fluorine atom. However, A f13 and A f14 At least one of L has a fluorine atom. 5 , A f13 and A f14 The total number of carbon atoms in the molecule is limited to 20.

[0158] L 5 The alkanediyl group in a41 The same as those exemplified for the alkanediyl group The following groups are mentioned:

[0159] A f13 The divalent saturated hydrocarbon group which may have a fluorine atom in or a divalent chain saturated hydrocarbon group which may have a fluorine atom and a It is preferably a divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalkane dialkyl group. It is a aryl group. Examples of the divalent chain saturated hydrocarbon group which may have a fluorine atom include a methylene group, an ethylene group, Alkanediyl groups such as diphenylene, propanediyl, butanediyl and pentanediyl groups Difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluoroalkanes such as perfluorobutanediyl and perfluoropentanediyl groups Examples thereof include a diyl group. The divalent alicyclic saturated hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexane group. Examples of the polycyclic group include an adamantanediyl group, a norbornyl group, and the like. Examples thereof include a nanediyl group and a perfluoroadamantanediyl group.

[0160] A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are represented by R a42 in The same groups as those exemplified above can be mentioned. Among them, trifluoromethyl group, difluoromethyl group, ethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1 ,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3, 3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2, 2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2 ,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group , perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and perfluorohexyl group. Fluorinated alkyl groups such as fluorooctyl group, cyclopropylmethyl group, cyclopropyl group , cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group xyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantyl group A methyl group and the like are preferred.

[0161] In formula (a4-3), L 5 is preferably an ethylene group. A f13 The divalent saturated hydrocarbon group is a divalent chain saturated hydrocarbon group having 1 to 6 carbon atoms and A group containing a divalent alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms is preferred, and a divalent chain having 2 to 3 carbon atoms is preferred. Saturated hydrocarbon groups of the formula are more preferred. A f14 The saturated hydrocarbon group is a chain saturated hydrocarbon group having 3 to 12 carbon atoms and Preferred are groups containing an alicyclic saturated hydrocarbon group such as More preferred is a group containing an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms. f14 teeth Preferably, it is a group containing an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably, Cyclopropylmethyl group, cyclopentyl group, cyclohexyl group, norbornyl group and a It is a damantyl group.

[0162] Examples of the structural unit represented by formula (a4-3) include the structural units represented by formulae (a4-1'-1) to (a 4-1'-11) are examples of structural units represented by the structural unit (a4-3). R f7 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-3). It is one of the structural units that can be mentioned.

[0163] The structural unit (a4) also includes a structural unit represented by the formula (a4-4). TIFF0007624483000101.tif4466[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 is -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 -or-(CH2) j4 - CO-O-(CH2) j5 - represents. j1 to j5 each independently represent an integer of 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms and containing a fluorine atom.]

[0164] R f22 The saturated hydrocarbon group of R a42 The saturated hydrocarbon groups represented by the formula: .R f22 is an alkyl group having 1 to 10 carbon atoms and a fluorine atom, or An alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms and a fluorine atom is preferred. An alkyl group is more preferred, and an alkyl group having 1 to 6 carbon atoms and a fluorine atom is even more preferred. It is nice. In formula (a4-4), A f21 As an example, -(CH2) j1 - is preferred, and ethylene A group or a methylene group is more preferred, and a methylene group is even more preferred.

[0165] Examples of the structural unit represented by formula (a4-4) include the following structural units and In the structural unit represented by the formula (a4-4), R f21 The methyl group corresponding to Examples of structural units include those in which hydrogen atoms are replaced by aryl groups. TIFF0007624483000102.tif87160

[0166] When the resin (A) has the structural unit (a4), its content is determined based on the total structural units of the resin (A). The ratio is preferably 1 to 20 mol %, more preferably 2 to 15 mol %, and more preferably 3 to 10 mol %. % is more preferred.

[0167] <Structural unit (a5)> The non-leaving hydrocarbon group contained in the structural unit (a5) is a straight-chain, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group. The group is preferred. Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1): . TIFF0007624483000103.tif3149[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the water contained in the alicyclic hydrocarbon group The atom may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms. L 55 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The -CH2- contained in the formula (I) may be replaced with -O- or -CO-.

[0168] R 52 The alicyclic hydrocarbon group in may be either a monocyclic or polycyclic group. Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentene group, and the like. Examples of the polycyclic alicyclic hydrocarbon group include, for example, , adamantyl group and norbornyl group. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Propyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl Examples of the alkyl group include an octyl group and a 2-ethylhexyl group. Examples of the alicyclic hydrocarbon group having a substituent include a 3-methyladamantyl group. do. R 52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably Examples thereof include an adamantyl group, a norbornyl group, and a cyclohexyl group.

[0169] L 55 The divalent saturated hydrocarbon group in the formula (I) is a divalent chain saturated hydrocarbon group or a divalent fatty acid group. Examples of the hydrocarbon group include cyclic saturated hydrocarbon groups, and preferably divalent chain saturated hydrocarbon groups. Examples of the divalent chain saturated hydrocarbon group include a methylene group, an ethylene group, and a propanediyl group. Examples of the alkyl groups include alkanediyl groups such as dialkyl groups, butanediyl groups, and pentanediyl groups. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the saturated hydrocarbon group include cyclopentanediyl and cyclohexanediyl groups. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include adatomyl groups. Examples thereof include a manthanediyl group and a norbornanediyl group.

[0170] L 55 The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula (I) is replaced by -O- or -CO-. Examples of the substituted groups include groups represented by formulae (L1-1) to (L1-4). In the following formula, * and ** each represent a bonding site, and * represents a bonding site with an oxygen atom. TIFF0007624483000104.tif17165 formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents L x1 It represents the binding site with ). L x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, L x1 and L x2 The total number of carbon atoms is 16 or less. In formula (L1-2), L x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms. L x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, L x3 and L x4 The total number of carbon atoms is 17 or less. In formula (L1-3), L x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. L x6 and L x7 each independently represents a single bond or a divalent aliphatic saturated carbon atom having 1 to 14 carbon atoms; Represents a hydrogen group. However, L x5 , L x6 and L x7 The total number of carbon atoms is 15 or less. In formula (L1-4), L x8 and L x9 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms. However, L x8 , L x9and W x1 The total number of carbon atoms is 15 or less. L x1 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably It is a methylene group or an ethylene group. L x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably Preferably, it is a single bond. L x3 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x5 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably It is a methylene group or an ethylene group. L x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably A methylene group or an ethylene group is preferred. L x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably Preferably, it is a single bond or a methylene group. L x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably Preferably, it is a single bond or a methylene group. W x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably , a cyclohexanediyl group, or an adamantanediyl group.

[0171] Examples of the group represented by formula (L1-1) include the divalent groups shown below. TIFF0007624483000105.tif53136

[0172] Examples of the group represented by formula (L1-2) include the divalent groups shown below. TIFF0007624483000106.tif24130

[0173] Examples of the group represented by formula (L1-3) include the divalent groups shown below. TIFF0007624483000107.tif15145

[0174] Examples of the group represented by formula (L1-4) include the divalent groups shown below. TIFF0007624483000108.tif26115

[0175] L 55 is preferably a single bond or a group represented by formula (L1-1).

[0176] The structural unit (a5-1) may be any of the structural units shown below and the structural units ( R in a5-1) 51 The structural unit in which the methyl group corresponding to the can be. TIFF0007624483000109.tif113151 When the resin (A) has the structural unit (a5), the content of the structural unit (a5) is determined based on the total structural units of the resin (A). The ratio is preferably 1 to 30 mol %, more preferably 2 to 20 mol %, and more preferably 3 to 15 mol %. % is more preferred.

[0177] <Structural unit (II)> The resin (A) further includes a structural unit that decomposes upon exposure to generate an acid (hereinafter, “structural unit The structural unit (II) may be specifically Examples of structural units include those described in JP 2016-79235 A, and the structural units include those having a sulfonate group on the side chain. A structural unit having a group or a carboxylate group and an organic cation, or a sulfonio group on a side chain It is preferably a structural unit having a group and an organic anion.

[0178] A structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain is preferably a structural unit represented by formula (II-2-A'). TIFF0007624483000110.tif3189 [In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The -CH2- contained in the saturated carbon atom may be replaced by -O-, -S- or -CO-. The hydrogen atom contained in the hydrogen hydride group is a halogen atom, a carbon number which may have a halogen atom It may be substituted with 1 to 6 alkyl groups or hydroxy groups. A x1 represents an alkanediyl group having 1 to 8 carbon atoms, and the water contained in the alkanediyl group The nitrogen atom may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. stomach. RA - represents a sulfonate group or a carboxylate group. R III3 is a hydrogen atom, a halogen atom, or a carbon atom having 1 Represents an alkyl group of 1 to 6. Z.A. + represents an organic cation.

[0179] R III3 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples include an uran atom. R III3 The alkyl group having 1 to 6 carbon atoms and optionally having a halogen atom is represented by the formula: R a8The same as an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, represented by the formula: Examples include the following. A x1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, , propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group group, hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4- Diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group Examples of the aryl group include pentane-1,4-diyl group and 2-methylbutane-1,4-diyl group. do. A x1 wherein the hydrogen atom in the formula (I) is optionally substituted, Examples of the group include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, Perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, Perfluoro tert-butyl group, perfluoropentyl group, perfluorohexyl group, etc. Some examples include:

[0180] X III3 The divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by the formula (I) is a straight-chain or branched and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. It may be a combination of the above. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1, 2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane- 1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, Linear alkanediyl groups such as decane-1,12-diyl group; butane-1,3-diyl group; 2-Methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentamethylpropane Branched alkanediyl groups such as 2-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. ru radical; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane -1,4-diyl group, cycloalkanediyl group such as cyclooctane-1,5-diyl group, etc. a divalent monocyclic alicyclic saturated hydrocarbon radical; Norbornane-1,4-diyl group, Norbornane-2,5-diyl group, Adamantane-1 Divalent polycyclic alicyclic saturated hydrocarbons such as 2,5-diyl group, adamantane-2,6-diyl group, etc. groups, etc.

[0181] A saturated hydrocarbon group in which -CH2- has been replaced with -O-, -S- or -CO- Examples of the divalent group include those represented by the formulae (X1) to (X53). The -CH2- contained in the saturated hydrocarbon group is replaced with -O-, -S- or -CO-. The number of carbon atoms in front of each is 17 or less. In the following formula, * and ** represent binding sites. * is A x1 represents the binding site with TIFF0007624483000111.tif144161

[0182] X 3 represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. X 4 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. X 5 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. X6 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 7 represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 8 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

[0183] Z.A. + The organic cation represented by the formula (B1) is the cation Z1 in the salt (B1). + Something similar to Some examples include:

[0184] The structural unit represented by the formula (II-2-A') is a structural unit represented by the formula (II-2-A) It is preferable that: TIFF0007624483000112.tif38109 [In formula (II-2-A), R III3 , X III3 and Z.A. + has the same meaning as above vinegar. z represents an integer of 0 to 6. R III2 and R III4 each independently represents a hydrogen atom, a fluorine atom, or a carbon atom represents a perfluoroalkyl group having a number of 1 to 6, and when z is 2 or more, a plurality of R III2 and R II I4 may be the same or different from each other. Q a and Q b each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents the alkyl group.

[0185] R III2 , R III4 , Q a and Q b Perfluoroalkyl groups having 1 to 6 carbon atoms, represented by the formula: The Q group is b1 The same as the perfluoroalkyl group having 1 to 6 carbon atoms represented by the formula: The following are some of the reasons.

[0186] The structural unit represented by formula (II-2-A) is a structural unit represented by formula (II-2-A-1). It is preferable that the position is 1. TIFF0007624483000113.tif5576 [In formula (II-2-A-1), R III2 , R III3 , R III4 , Q a , Q b , z and Z A + has the same meaning as above represent. R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. X I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, The -CH2- may be replaced by -O-, -S- or -CO-, and the saturated hydrocarbon may be The hydrogen atoms contained in the radicals may be substituted with halogen atoms or hydroxy groups.

[0187] R III5 Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, and the like. , propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and and dodecyl group. X I2 As the divalent saturated hydrocarbon group represented by the formula: III3 Divalent saturated carbon represented by The same as the hydride group can be mentioned.

[0188] The structural unit represented by formula (II-2-A-1) is preferably a structural unit represented by formula (II-2-A-2). The structural unit is preferably TIFF0007624483000114.tif5287 [In formula (II-2-A-2), R III3 , R III5 and Z.A. + has the same meaning as above Represents. m and n each independently represent 1 or 2.

[0189] Examples of the structural unit represented by formula (II-2-A') include the following structural units and the International Examples of the structural units include those described in Publication No. 2012 / 050015. + is an organic cation Represents. TIFF0007624483000115.tif131155

[0190] TIFF0007624483000116.tif83134

[0191] The structural unit having a sulfonio group and an organic anion in the side chain is represented by the formula (II-1-1): It is preferable that the structural unit is a structural unit that is TIFF0007624483000117.tif3281 [In formula (II-1-1), A II1 represents a single bond or a divalent linking group. R II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R II2 and R II3 each independently represents a hydrocarbon group having 1 to 18 carbon atoms; R II2 and R II3 are bonded together to form a ring with the sulfur atom to which they are attached. This is also fine. R II4 is a hydrogen atom, a halogen atom, or a group having 1 to 10 carbon atoms which may have a halogen atom Represents an alkyl group of 6. A - represents an organic anion. R II1As the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by the formula (I), a phenylene group is preferable. and naphthylene groups. R II2 and R II3 Examples of the hydrocarbon group represented by the formula (I) include an alkyl group and an alicyclic hydrocarbon group. , aromatic hydrocarbon groups, and groups formed by combining these groups. Examples of the alkyl group and the alicyclic hydrocarbon group include the same as those mentioned above. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples of the aryl group include a phenanthryl group. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. , aralkyl groups such as benzyl groups, aromatic hydrocarbon groups having alkyl groups (p-methylphenyl nyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group phenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), alicyclic carbon Aromatic hydrocarbon groups having a hydride group (p-cyclohexylphenyl group, p-adamantyl phenyl group, phenylcyclohexyl group, and other aryl-cycloalkyl groups. can be. R II4 The halogen atom represented by the formula (I) is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Examples of such atoms include elementary atoms. R II4 As an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, represented by is R a8 The same as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom and which is represented by the formula: Some examples include: A II1 Examples of the divalent linking group represented by the formula (I) include a divalent saturated carbon atom having 1 to 18 carbon atoms. The -CH2- contained in the divalent saturated hydrocarbon group is -O-, -S- or may be replaced by -CO-. Specifically, X III3 The carbon number is 1 to 1 Examples of the divalent saturated hydrocarbon group include the same as those in 8.

[0192] The structural unit containing a cation in formula (II-1-1) may be any of the structural units represented by the following formula: Some examples include: TIFF0007624483000118.tif79144

[0193] TIFF0007624483000119.tif100140

[0194] A - As the organic anion represented by the formula (I), a sulfonate anion, a sulfonylimide anion, Examples of the anion include sulfonylmethide anion and carboxylate anion. - Represented by The organic anion is preferably a sulfonate anion, and more preferably a sulfonate anion or a sulfonylimide anion. As the anion, the sulfonylmethide anion and the carboxylate anion, those represented by the above formula ( The anions may be the same as those contained in the salt represented by I).

[0195] Examples of the structural unit represented by formula (II-1-1) include the structural units represented by the following formula: can be done. TIFF0007624483000120.tif159140

[0196] When the resin (A) contains the structural unit (II), the content of the structural unit (II) is It is preferably 1 to 20 mol %, more preferably 2 to 4 mol %, based on the total structural units of the oil (A). It is 15 mol %, and more preferably 3 to 10 mol %.

[0197] The resin (A) may have structural units other than the above-mentioned structural units. The positions include structural units known in the art. The resin (A) is preferably a resin composed of the structural unit (a1) and the structural unit (s), i.e. That is, it is a copolymer of monomer (a1) and monomer (s). The structural unit (a1) is preferably a structural unit (a1-0), a structural unit (a1-1) and a structural unit (a1-2). The structural unit (a1-2) (preferably a cyclohexyl group or a structural unit having a cyclopentyl group) At least one selected from the group consisting of structural units, more preferably at least two and more preferably, the group consisting of the structural unit (a1-1) and the structural unit (a1-2). At least two selected from the above. The structural unit (s) is preferably selected from the group consisting of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably represented by the formula (a2-1): The structural unit (a3) ​​is preferably a structural unit represented by the formula (a2-A). or a structural unit represented by formula (a3-1), a structural unit represented by formula (a3-2) and a structural unit represented by formula (a3-3) a3-4) is at least one selected from the group consisting of structural units represented by the following formula:

[0198] Each structural unit constituting the resin (A) may be used alone or in combination of two or more. Instead, monomers that lead to these structural units are used in known polymerization methods (e.g., radical polymerization methods). The content of each structural unit in the resin (A) can be determined by the following procedure. This can be adjusted by the amount of monomer used. The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more). 00 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30 In the present specification, the weight average molecular weight is preferably 1,000 or less, and more preferably 15,000 or less. The molecular weight is a value determined by gel permeation chromatography under the conditions described in the Examples. It is.

[0199] <Resins other than resin (A)> The resist composition of the present invention contains, in addition to the resin (A), a resin other than the resin (A). Good too. Examples of the resin other than the resin (A) include a resin containing the structural unit (a4) or the structural unit (a5). (hereinafter, may be referred to as resin (X)).

[0200] As the resin (X), a resin containing the structural unit (a4) is particularly preferred. In resin (X), the content of the structural unit (a4) is the sum of all structural units in resin (X). It is preferably 30 mol % or more, and more preferably 40 mol % or more. It is more preferable that the content is 45 mol % or more. Examples of the structural unit that the resin (X) may further have include the structural unit (a2), the structural unit (a3) and structural units derived from other known monomers. X) is preferably a resin consisting of only the structural unit (a4) and / or the structural unit (a5). It is preferable that the resin is composed only of the structural unit (a4).

[0201] Each structural unit constituting the resin (X) may be used alone or in combination of two or more kinds. Using monomers that derive these structural units, a known polymerization method (e.g., radical polymerization method) is performed. The content of each structural unit in the resin (X) can be determined by the following procedure. This can be adjusted by the amount of monomer used. The weight average molecular weight of each of the resins (X) is preferably 6,000 or more (more preferably 6,000 or more). Preferably 7,000 or more), 80,000 or less (more preferably 60,000 or less). The method for measuring the weight average molecular weight of the resin (X) is the same as that for the resin (A). When the resist composition contains resin (X), the content thereof is The content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, and further The amount is preferably 1 to 40 parts by mass, particularly preferably 1 to 30 parts by mass, and particularly preferably is 1 to 8 parts by mass.

[0202] The content of the resin (A) in the resist composition is 8 to 100% based on the solid content of the resist composition. It is preferably 0% by mass or more and 99% by mass or less, and more preferably 90% by mass or more and 99% by mass or less. In addition, when a resin other than the resin (A) is contained, the resin (A) and the resin other than the resin (A) are preferably mixed. The total content of the resin is 80% by mass or more and 99% by mass or less based on the solid content of the resist composition. It is preferable that the content is 90% by mass or less, and more preferable that the content is 90% by mass or more and 99% by mass or less. In the present specification, the term "solid content of the resist composition" refers to the amount of the solvent (E The solid content of the resist composition and the resin content The rate is measured by known analytical means such as liquid chromatography or gas chromatography. It is possible.

[0203] <Solvent (E)> The content of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less. It is preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more. The content of the solvent (E) is 99% by mass or less. The content of the solvent (E) is measured, for example, by liquid chromatography or gas chromatography. This can be measured by known analytical means such as chromatography. The solvent (E) may be ethyl cellosolve acetate, methyl cellosolve acetate, or Glycol ether esters such as propylene glycol monomethyl ether acetate ; Glycol ethers such as propylene glycol monomethyl ether; Ethyl lactate, acetic acid esters such as butyl acetate, amyl acetate, and ethyl pyruvate; acetone, methyl isobutyl ketones such as cyclohexanone, 2-heptanone, and cyclohexanone; cyclic esters; etc. One type of solvent (E) may be used alone, Two or more types may be used.

[0204] <Quencher (C)> The quencher (C) may be a basic nitrogen-containing organic compound or an acid generator (B). The salts that generate acids with weaker acidity than the acid generated are listed below. is preferably about 0.01 to 5 mass % based on the solid content of the resist composition. . Examples of basic nitrogen-containing organic compounds include amines and ammonium salts. The amines include aliphatic amines and aromatic amines. The aliphatic amines include primary Amines include secondary amines and tertiary amines. Amines include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylamine, aniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline Phosphorus, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine , octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, Dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine amine, triethylamine, trimethylamine, tripropylamine, tributylamine, Tripentylamine, trihexylamine, triheptylamine, trioctylamine, Trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine , methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, Methyldioctylamine, Methyldinonylamine, Methyldidecylamine, Ethyldibutyrate diamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine , ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylamine xylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropylamine Propanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine amine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3' -Dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridinium 4-Methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl)ethane 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-Di(4-pyridyl)propane, 1,2-Di(4-pyridyloxy)ethane, Di( 2-Pyridyl) ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide amine, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. Among them, preferred are aromatic amines such as diisopropylaniline, and more preferred are aromatic amines such as diisopropylaniline. Examples include 2,6 - diisopropyl aniline. Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexyl ammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3 - (trifluoromethyl)phenyltrimethylammonium hydroxide, tetra - n - butylammonium salicylate, choline, and the like. are mentioned.

[0205] The acidity of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). The salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is a salt with an acid dissociation constant of the acid generated from the salt usually being - 3 < pKa, preferably a salt with - 1 < pKa < 7, and more preferably a salt with 0 < pKa < 5. Examples of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) include the salts represented by the following formula, the salts represented by formula (D) described in JP - A - 2015 - 147926 (hereinafter sometimes referred to as "weak acid inner salt (D)"), and the salts described in JP - A - 2012 - 229206 JP - A - 2012 - 6908, JP - A - 2012 - 72109, JP - A - 2011 - 3 9502, and JP - A - 2011 - 191745. Preferred as the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is the weak acid inner salt (D). (B) is preferably the weak acid inner salt (D). TIFF0007624483000121.tif113147

[0206] Examples of the weak acid inner salt (D) include the following salts. TIFF0007624483000122.tif95145

[0207] When the resist composition contains a quencher (C), the content of the quencher (C) is The amount of the photosensitive resin is usually from 0.01 to 5 mass %, preferably from 0.01 to 5 mass %, based on the solid content of the resist composition. It is 3% by mass.

[0208] <Other Ingredients> The resist composition of the present invention may further contain components other than the above-mentioned components (hereinafter referred to as “other components”) as necessary. (F)) may be contained. There are no particular limitations on other components (F). However, additives known in the resist art, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, etc., may be used. Agents, dyes, etc. can be used.

[0209] Preparation of Resist Composition The resist composition of the present invention comprises a salt (I) and a resin (A), and, if necessary, an acid generator. Agent (B), resin other than resin (A), solvent (E), quencher (C) and other components ( F). The order of mixing is arbitrary and is not particularly limited. The temperature during mixing ranges from 10 to 40°C, depending on the type of resin, solvent, etc. The appropriate temperature can be selected depending on the solubility of the mixture in E). The mixing time depends on the mixing temperature. Depending on the situation, an appropriate time can be selected from 0.5 to 24 hours. There is no limitation on the type of the mixture, and stirring and mixing can be used. After mixing the components, filter the mixture using a filter with a pore size of about 0.003 to 0.2 μm. It is preferable that

[0210] <Method for Producing Resist Pattern> The method for producing a resist pattern of the present invention comprises the steps of: (1) applying the resist composition of the present invention onto a substrate; (2) A step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) A step of developing the composition layer after heating. To apply the resist composition onto a substrate, a commonly used device such as a spin coater is used. The substrate can be an inorganic substrate such as a silicon wafer. Before applying the resist composition, the substrate may be cleaned, and an anti-reflection film or the like may be formed on the substrate. It may be possible. The composition after coating is dried to remove the solvent and form a composition layer. For example, the solvent can be evaporated using a heating device such as a hot plate (so-called prebaking). The heating temperature is 50 to 200°C. It is preferable that the heating time is 10 to 180 seconds. The pressure during the process is 1 to 1.0×10 5 It is preferable that the pressure is about Pa. The obtained composition layer is usually exposed using an exposure machine. The exposure light source may be a KrF excimer laser (wavelength 248 nm), an ArF excimer Lasers in the ultraviolet range such as F2 excimer laser (wavelength 157 nm) and F2 laser (wavelength 193 nm) Laser light emitted from a solid-state laser light source (YAG or semiconductor laser, etc.) Those that convert the wavelength and emit harmonic laser light in the far ultraviolet or vacuum ultraviolet range, electron beams, Various types of light sources can be used, such as those that irradiate ultraviolet light (EUV). In this case, the irradiation of these radiations is sometimes collectively called "exposure". Exposure is usually carried out through a mask corresponding to the desired pattern. In the case of lines, exposure may be performed by direct writing without using a mask.

[0211] The composition layer after exposure is subjected to a heat treatment (so-called heat treatment) in order to promote the deprotection reaction of the acid labile group. The heating temperature is usually about 50 to 200°C, preferably The temperature is usually around 70 to 150 degrees Celsius. The composition layer after heating is usually developed using a developing device and a developing solution. Examples of the method include the dip method, the paddle method, the spray method, and the dynamic dispense method. The development temperature is preferably, for example, 5 to 60° C., and the development time is, for example, 5 The time is preferably 300 seconds or less. By selecting the type of developer as follows: Either a positive resist pattern or a negative resist pattern can be produced.

[0212] When a positive resist pattern is produced from the resist composition of the present invention, a developer An alkaline developer is used. The alkaline developer is any of the various alkaline solutions used in this field. Any solution is acceptable. For example, tetramethylammonium hydroxide or (2-hydroxy Examples of the aqueous solution ... ethyl)trimethylammonium hydroxide (commonly known as choline) include aqueous solutions of ethyl)trimethylammonium hydroxide (commonly known as choline). The alkaline developer may contain a surfactant. After development, the resist pattern is washed with ultrapure water, and then the water remaining on the substrate and pattern is It is preferable to remove it. When a negative resist pattern is produced from the resist composition of the present invention, A developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used. The organic solvents contained in organic developers are ketones such as 2-hexanone and 2-heptanone. Solvents; glycol ether ethers such as propylene glycol monomethyl ether acetate Steryl solvents; ester solvents such as butyl acetate; propylene glycol monomethyl ether, etc. glycol ether solvents; amide solvents such as N,N-dimethylacetamide; anisole and the like aromatic hydrocarbon solvents. In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less. The content is preferably from 95% by mass to 100% by mass, and more preferably substantially only an organic solvent. More preferred. Among them, organic developers include those containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass. Preferably, the content is 90% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less. It is even more preferred that the components are qualitatively butyl acetate and / or 2-heptanone only. The organic developer may contain a surfactant. The water content may be less than 10%. During development, development is stopped by replacing the organic developer with a different type of solvent. Good too. It is preferable to wash the resist pattern after development with a rinse solution. There are no particular limitations as long as the solvent does not dissolve the resist pattern, and any solvent containing a general organic solvent may be used. Any suitable solvent may be used, preferably an alcohol or ester solvent. After cleaning, it is preferable to remove any rinsing liquid remaining on the substrate and the pattern.

[0213] <Application> The resist composition of the present invention is a resist composition for exposure to a KrF excimer laser, Resist composition for exposure to ximer laser, resist composition for exposure to electron beam (EB) or EU A resist composition for V exposure, particularly a resist composition for electron beam (EB) exposure or EUV exposure The composition is suitable as a resist composition for semiconductor microfabrication. EXAMPLES

[0214] The present invention will be described in more detail with reference to examples. "%" and "parts" are by weight unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography. The analytical conditions for gel permeation chromatography are as follows: Column: TSKgel Multipore HXL-M x 3 + guard column (Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (Tosoh Corporation) The structure of the compound was determined by mass spectrometry (LC: Agilent 1100, MASS: Agilent The molecular ion peak was measured using a LC / MSD (manufactured by Entec). In the examples, the value of this molecular ion peak is indicated as "MASS."

[0215] Example 1: Synthesis of a salt represented by formula (I-2) TIFF0007624483000123.tif55142 5 parts of the compound represented by formula (I-2-a), 10 parts of tetrahydrofuran and trifluoro 11.00 parts of trimethylsilyl methanesulfonate was mixed and stirred at 23°C for 30 minutes. The mixture was cooled to 10° C. and 1.20 parts of magnesium, 8 parts of compound represented by formula (I-2-b) Grignard produced by mixing 0.65 parts of ethyl alcohol and 17.30 parts of tetrahydrofuran. The resulting solution was added dropwise to the previously obtained mixed solution at 10°C, and the mixture was stirred at 23°C for 18 hours. 30 parts of 1N hydrochloric acid and 50 parts of chloroform were added to the resulting reaction mixture and the mixture was stirred at 23°C for 3 hours. After stirring for 10 minutes, the organic layer was separated and separated. The organic layer was added with 30 parts of ion-exchanged water. After adding the water and stirring at 23°C for 30 minutes, the organic layer was separated and taken out. The organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether. Add 30 parts of tert-butyl ether, stir at 23°C for 30 minutes, remove the supernatant, and concentrate. As a result, 3.24 parts of a salt represented by the formula (I-2-c) was obtained. TIFF0007624483000124.tif43165 2.91 parts of a salt represented by formula (I-2-c), 2.56 parts of a salt represented by formula (I-2-d) 15 parts of chloroform and 30 parts of ion-exchanged water were mixed and stirred at 23°C for 2 hours. The organic layer was extracted by distillation. 15 parts of 1N hydrochloric acid was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes. After stirring for 1 hour, the organic layer was separated and separated. 15 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed five times. The obtained organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether. Add 30 parts of the mixture, stir at 23°C for 30 minutes, remove the supernatant, and concentrate. As a result, 1.62 parts of the salt represented by formula (I-2) was obtained. MASS(ESI(+)Spectrum):M + 353.0 MASS(ESI(-)Spectrum):M - 339.1

[0216] Example 2: Synthesis of a salt represented by formula (I-3) TIFF0007624483000125.tif45165 2.91 parts of salt represented by formula (I-2-c), 2.46 parts of salt represented by formula (I-3-d) 15 parts of chloroform and 30 parts of ion-exchanged water were mixed and stirred at 23°C for 2 hours. The organic layer was extracted by distillation. 15 parts of 1N hydrochloric acid was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes. After stirring for 1 hour, the organic layer was separated and separated. 15 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed five times. The obtained organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether. Add 30 parts of the mixture, stir at 23°C for 30 minutes, remove the supernatant, and concentrate. As a result, 1.72 parts of the salt represented by formula (I-3) was obtained. MASS(ESI(+)Spectrum):M + 353.0 MASS(ESI(-)Spectrum):M - 323.0

[0217] Example 3: Synthesis of a salt represented by formula (I-14) TIFF0007624483000126.tif45165 2.91 parts of a salt represented by formula (I-2-c), 2.46 parts of a salt represented by formula (I-14-d) 15 parts of chloroform and 30 parts of ion-exchanged water were mixed and stirred at 23°C for 2 hours. The organic layer was separated and extracted. 15 parts of 1N hydrochloric acid was added to the obtained organic layer and the mixture was stirred at 23° C. for 30 minutes. After stirring for 10 minutes, the mixture was separated to separate the organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed five times. The obtained organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether. After adding 30 parts of ethyl alcohol and stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated. As a result, 2.32 parts of the salt represented by the formula (I-14) was obtained. MASS(ESI(+)Spectrum):M + 353.0 MASS(ESI(-)Spectrum):M - 323.1

[0218] Example 4: Synthesis of a salt represented by formula (I-43) TIFF0007624483000127.tif57142 5 parts of the compound represented by formula (I-2-a), 10 parts of tetrahydrofuran and trifluoro 11.00 parts of trimethylsilyl methanesulfonate was mixed and stirred at 23°C for 30 minutes. and cooled to 10° C. 1.20 parts of magnesium, a compound represented by formula (I-43-b) Grignard produced by mixing 10.43 parts of ethyl alcohol and 20.86 parts of tetrahydrofuran. The shale solution was added dropwise to the previously obtained mixed solution at 10°C, and the mixture was stirred at 23°C for 18 hours. To the resulting reaction mixture, 30 parts of 1N hydrochloric acid and 50 parts of chloroform were added and the mixture was heated to 23°C. After stirring for 30 minutes at 40°C, the mixture was separated to separate the organic layer. After adding 100 parts of the mixture and stirring at 23°C for 30 minutes, the organic layer was separated and taken out. The above procedure was repeated three times. The obtained organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl 30 parts of ether was added, and the mixture was stirred at 23°C for 30 minutes. The supernatant was removed and the mixture was concentrated. As a result, 3.11 parts of a salt represented by the formula (I-43-c) was obtained. TIFF0007624483000128.tif45165 3.12 parts of a salt represented by formula (I-43-c), 2.4 parts of a salt represented by formula (I-14-d) Mix 6 parts of chloroform, 15 parts of chloroform and 30 parts of ion-exchanged water, and stir at 23°C for 2 hours. The organic layer was separated and the organic layer was taken out. 15 parts of 1N hydrochloric acid was added to the obtained organic layer and the mixture was stirred at 23° C. for 3 After stirring for 10 minutes, the organic layer was separated and separated. The organic layer was added with 15 parts of ion-exchanged water. After adding the water and stirring at 23°C for 30 minutes, the organic layer was separated and taken out. The organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether. Add 30 parts of tert-butyl ether, stir at 23°C for 30 minutes, remove the supernatant, and concentrate. As a result, 1.91 parts of a salt represented by the formula (I-43) was obtained. MASS(ESI(+)Spectrum):M + 389.0 MASS(ESI(-)Spectrum):M - 323.1

[0219] Example 5: Synthesis of a salt represented by formula (I-72) TIFF0007624483000129.tif53142 5 parts of the compound represented by formula (I-2-a), 10 parts of tetrahydrofuran and trifluoro 11.00 parts of trimethylsilyl methanesulfonate was mixed and stirred at 23°C for 30 minutes. and cooled to 10° C. 1.20 parts of magnesium, a compound represented by formula (I-72-b) Grigna produced by mixing 9.54 parts of tetrahydrofuran and 19.08 parts of tetrahydrofuran The mixture was added dropwise to the previously obtained mixed solution at 10°C, and then stirred at 23°C for 18 hours. To the resulting reaction mixture, 30 parts of 1N hydrochloric acid and 50 parts of chloroform were added and the mixture was stirred at 23°C. After stirring for 30 minutes, the organic layer was separated and extracted. After adding the water, the mixture was stirred at 23°C for 30 minutes, and the organic layer was separated. The organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether. Add 30 parts of ether, stir at 23°C for 30 minutes, remove the supernatant, and concentrate. This gave 1.09 parts of a salt represented by the formula (I-72-c). TIFF0007624483000130.tif45164 1.01 parts of a salt represented by formula (I-72-c), 0.8 parts of a salt represented by formula (I-14-d) 2 parts of chloroform, 10 parts of ion-exchanged water, and 20 parts of ethyl acetate were mixed and stirred at 23°C for 2 hours. The organic layer was separated and the organic layer was taken out. 10 parts of 1N hydrochloric acid was added to the obtained organic layer and the mixture was stirred at 23° C. for 3 After stirring for 10 minutes, the organic layer was separated and separated. The organic layer was added with 10 parts of ion-exchanged water. After adding the water and stirring at 23°C for 30 minutes, the organic layer was separated and taken out. The organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether. Add 20 parts of tert-butyl ether, stir at 23°C for 30 minutes, remove the supernatant, and concentrate. As a result, 0.42 parts of a salt represented by the formula (I-72) was obtained. MASS(ESI(+)Spectrum):M + 371.0 MASS(ESI(-)Spectrum):M - 323.1

[0220] Example 6: Synthesis of salt represented by formula (I-13) TIFF0007624483000131.tif41161 2.91 parts of a salt represented by formula (I-2-c), 3.29 parts of a salt represented by formula (I-13-d) 15 parts of chloroform and 30 parts of ion-exchanged water were mixed and stirred at 23°C for 2 hours. The organic layer was separated and extracted. 15 parts of 1N hydrochloric acid was added to the obtained organic layer and the mixture was stirred at 23° C. for 30 minutes. After stirring for 10 minutes, the mixture was separated to separate the organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed five times. The obtained organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether. After adding 30 parts of ethyl alcohol and stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated. As a result, 2.11 parts of the salt represented by the formula (I-13) was obtained. MASS(ESI(+)Spectrum):M + 353.0 MASS(ESI(-)Spectrum):M - 467.1

[0221] Example 7: Synthesis of a salt represented by formula (I-15) TIFF0007624483000132.tif43168 2.91 parts of a salt represented by formula (I-2-c), 2.56 parts of a salt represented by formula (I-15-d) 15 parts of chloroform and 30 parts of ion-exchanged water were mixed and stirred at 23°C for 2 hours. The organic layer was separated and extracted. 15 parts of 1N hydrochloric acid was added to the obtained organic layer and the mixture was stirred at 23° C. for 30 minutes. After stirring for 10 minutes, the mixture was separated to separate the organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed five times. The obtained organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether. After adding 30 parts of ethyl alcohol and stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated. As a result, 1.89 parts of the salt represented by the formula (I-15) was obtained. MASS(ESI(+)Spectrum):M + 353.0 MASS(ESI(-)Spectrum):M - 339.1

[0222] Example 8: Synthesis of salt represented by formula (I-16) TIFF0007624483000133.tif45168 2.91 parts of a salt represented by formula (I-2-c), 2.55 parts of a salt represented by formula (I-16-d) 15 parts of chloroform and 30 parts of ion-exchanged water were mixed and stirred at 23°C for 2 hours. The organic layer was separated and extracted. 15 parts of 1N hydrochloric acid was added to the obtained organic layer and the mixture was stirred at 23° C. for 30 minutes. After stirring for 10 minutes, the mixture was separated to separate the organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed five times. The obtained organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether. After adding 30 parts of ethyl alcohol and stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated. As a result, 1.81 parts of the salt represented by the formula (I-16) was obtained. MASS(ESI(+)Spectrum):M + 353.0 MASS(ESI(-)Spectrum):M - 337.1

[0223] Example 9: Synthesis of a salt represented by formula (I-17) TIFF0007624483000134.tif41163 2.91 parts of a salt represented by formula (I-2-c), 3.39 parts of a salt represented by formula (I-17-d) 15 parts of chloroform and 30 parts of ion-exchanged water were mixed and stirred at 23°C for 2 hours. The organic layer was separated and extracted. 15 parts of 1N hydrochloric acid was added to the obtained organic layer and the mixture was stirred at 23° C. for 30 minutes. After stirring for 10 minutes, the mixture was separated to separate the organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed five times. The obtained organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether. After adding 30 parts of ethyl alcohol and stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated. As a result, 2.88 parts of the salt represented by the formula (I-17) was obtained. MASS(ESI(+)Spectrum):M + 353.0 MASS(ESI(-)Spectrum):M - 481.1

[0224] Resin synthesis The compounds (monomers) used in the synthesis of resin (A) are shown below. are referred to as "monomer (a1-1-3)" etc. depending on their formula numbers. TIFF0007624483000135.tif3691

[0225] Synthesis Example 1 [Synthesis of Resin A1] As the monomer, monomer (a1-4-2), monomer (a1-1-3) and monomer (a1-2-6) was used, and the molar ratio [monomer (a1-4-2):monomer (a1-1 -3):monomer (a1-2-6) in a ratio of 38:24:38. Further, this monomer mixture was mixed with 1.5 times by mass of methyl ether based on the total mass of all monomers. Isobutyl ketone was mixed in the mixture. Azobisisobutyronite was added as an initiator to the mixture. The amount of each of these monomers was 7 mol % based on the total number of moles of all monomers. The mixture was heated at 85°C for about 5 hours to carry out polymerization. The mixture was stirred for 6 hours and then separated. The resin was precipitated by pouring it into n-heptane, and then filtered and collected to obtain a resin with a weight average molecular weight of about 5. .3×10 3 Resin A1 (copolymer) was obtained in a yield of 78%. It has structural units. TIFF0007624483000136.tif30125

[0226] Synthesis Example 2 [Synthesis of Resin A2] As the monomer, monomer (a1-4-2), monomer (a1-1-3) and monomer Monomer (a1-4-2): Monomer (a1-2-6) were used, and the molar ratio 1-3):monomer (a1-2-6) were mixed in a ratio of 49:21:30. Further, this monomer mixture was mixed with 1.5 times by mass of methyl based on the total mass of all monomers. The mixture was mixed with azobisisobutyronide as an initiator. tolyl was added in an amount of 7 mol% based on the total moles of all monomers, This was heated at 85° C. for about 5 hours to carry out polymerization. After that, p-toluene was added to the polymerization reaction solution. An aqueous solution of benzenesulfonic acid was added, and the mixture was stirred for 6 hours, after which the layers were separated. The resin was precipitated by pouring it into n-heptane and then filtering and recovering it, resulting in a weight average molecular weight of about 5.8×10 3 Resin A2 (copolymer) was obtained in a yield of 84%. It has the structural unit: TIFF0007624483000137.tif30125

[0227] Synthesis Example 3 [Synthesis of Resin AX1] As the monomers, monomer (a1-4-2) and monomer (a1-2-6) are used, The molar ratio of monomer (a1-4-2):monomer (a1-2-6) is 49:51. The monomer mixture is mixed in such a ratio that the total weight of all the monomers is Then, 1.5 times the mass of methyl isobutyl ketone was mixed into the mixture. The amount of azobisisobutyronitrile was 7 moles per mole of all monomers. %, and the mixture was heated at 85°C for about 5 hours to carry out polymerization. To the polymerization reaction solution, an aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 6 hours and then separated. The organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and collected. The weight average molecular weight is about 5.9×10 3 Resin AX1 (copolymer) was obtained with a yield of 88%. This resin AX1 has the following structural units: TIFF0007624483000138.tif2696

[0228] <Preparation of resist composition> As shown in Table 2, the following components were mixed, and the resulting mixture was passed through a fluorine-containing filter with a pore size of 0.2 μm. The mixture was filtered through a resin filter to prepare a resist composition.

[0229] [Table 2]

[0230] <Resin> A1, A2, AX1: Resin A1, Resin A2, Resin X1, Resin AX1 <Salt (I)> I-2: A salt represented by formula (I-2) I-3: A salt represented by formula (I-3) I-13: A salt represented by formula (I-13) I-14: A salt represented by formula (I-14) I-15: A salt represented by formula (I-15) I-16: A salt represented by formula (I-16) I-17: A salt represented by formula (I-17) I-43: A salt represented by formula (I-43) I-72: A salt represented by formula (I-72) <Acid generator> IX-1: A salt represented by formula (IX-1) (Example of JP 2017-015777 A) (synthesized according to TIFF0007624483000140.tif3466<Quencher(C)> C1: Synthesized by the method described in JP 2011-39502 A TIFF0007624483000141.tif4349<Solvent(E)> Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 100 parts γ-Butyrolactone 5 parts

[0231] (Electron beam exposure evaluation of resist composition) A 6-inch silicon wafer is heated on a direct hot plate with hexamethyldisilazane. The silicon wafer was treated at 90° C. for 60 seconds. The layer was spin-coated to a thickness of 0.04 μm. The substrate was prebaked for 60 seconds at the temperature shown in the "PB" column of Table 2 to form a composition layer. The composition layer formed on the wafer was then subjected to an electron beam lithography machine (HL-800D manufactured by Hitachi, Ltd.). A line and space pattern was created by changing the exposure dose stepwise using a laser with an energy of 50 keV. Directly painted. After exposure, post-exposure was performed for 60 seconds on a hot plate at the temperature shown in the "PEB" column of Table 2. The jar was baked and then immersed in 2.38% tetramethylammonium hydroxide aqueous solution. A resist pattern was obtained by puddle development in a solution for 60 seconds. The resulting resist pattern (line and space pattern) was observed with a scanning electron microscope. In other words, the line width and space width of the 60 nm line and space pattern are 1:1. The exposure amount at which the light was emitted was taken as the effective sensitivity.

[0232] Line Edge Roughness Evaluation (LER): Sidewall of resist pattern produced at effective sensitivity The amplitude of the unevenness of the surface was measured using a scanning electron microscope to obtain the line edge roughness. The results are shown in Table 3.

[0233] [Table 3]

[0234] From the above results, it can be seen that the salt of the present invention and the resist composition containing the salt can effectively prevent line edge roughness. It can be seen that the LER is good. [Industrial Applicability]

[0235] The salt of the present invention and the resist composition containing the salt have good line edge roughness and are semi-transparent. It is useful for microfabrication of conductors.

Claims

1. A resist composition comprising: an acid generator containing a salt represented by formula (I); a resin that contains a structural unit having an acid labile group and a structural unit represented by formula (a2-A); and a carboxylate that generates an acid having a weaker acidity than the acid generated from the acid generator. [In formula (I), R １ , R ２ , R ３ , R ４ and R ５ each independently represents a halogen atom or a perfluoroalkyl group having 1 to 6 carbon atoms. R ６ , R ７ and R ８ each independently represents a halogen atom, a hydroxyl group, a fluorinated alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 12 carbon atoms, and —CH 2 - may be replaced by -O- or -CO-. m5 represents an integer of 1 to 5, and when m5 is 2 or more, a plurality of R ５ may be the same or different from each other. m6 represents an integer of 0 to 3, and when m6 is 2 or more, a plurality of R ６ may be the same or different from each other. m7 represents an integer of 0 to 3, and when m7 is 2 or more, a plurality of R ７ may be the same or different from each other. m8 represents an integer of 0 to 4, and when m8 is 2 or more, a plurality of R ８ may be the same or different, provided that 1≦m5+m8≦5. AI － represents an anion represented by formula (IA). [In formula (IA), Q １ and Q. ２ each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L １ represents a saturated hydrocarbon group having 1 to 24 carbon atoms, and the —CH ２ - may be replaced by -O- or -CO-, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a fluorine atom or a hydroxy group. Y １ represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the —CH ２ - is -O-, -SO ２ - or -CO- may be substituted.] [In formula (a2-A), R a50 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or *-X a51 - (A a52 -X a52 ) nb -, * represents -R a50 represents the bonding site with the carbon atom to which it is bonded. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents an integer of 0 to 4. When mb is an integer of 2 or more, a plurality of R a51 may be the same or different.

2. 2. The resist composition according to claim 1, wherein the structural unit having an acid labile group comprises at least one of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2). [In formula (a1-1) and formula (a1-2), L ａ１ and L ａ２ are each independently -O- or *-O-(CH ２ ) ｋ１ represents --CO--O--, k1 represents an integer of 1 to 7, and * represents the bonding site with --CO--. R ａ４ and R ａ５ each independently represents a hydrogen atom or a methyl group. R ａ６ and R ａ７ each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3.

3. (1) a step of applying the resist composition according to claim 1 or 2 onto a substrate; (2) A step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) developing the composition layer after heating; A method for producing a resist pattern comprising the steps of:

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