Carboxylate, carboxylic acid generator, resist composition, and method for producing a resist pattern

Abstract

To provide a carboxylate, a carboxylic acid generator, and a resist composition capable of producing a resist pattern having good line edge roughness.SOLUTION: The carboxylate represented by formula (I), the carboxylic acid generator, and the resist composition are provided. [In the formula, R1 and R2 each independently represent an iodine atom, a fluorine atom or the like; R4, R5, R7 and R8 each independently represent a halogen atom, a hydroxy group, a C1-12 haloalkyl group or a C1-12 alkyl group, provided that -CH2- contained in the haloalkyl group and the alkyl group may be substituted with -O-, -CO- or the like; X1 and X2 each independently represent an oxygen atom or a sulfur atom; m1 represents an integer of 1-5, m2 and m8 each represent an integer of 0-5, and m4, m5 and m7 each represent an integer of 0-4, provided that 1≤m1+m7≤5 and 0≤m2+m8≤5; and X0 represents an optionally substituted hydrocarbon group.]SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a carboxylate, a carboxylic acid generator, a resist composition, and a method for producing a resist pattern.

Background Art

[0002] Patent Document 1 describes a resist composition containing a carboxylate represented by the following formula as a carboxylic acid generator. TIFF0007702806000001.tif1455Non-Patent Document 1 describes a salt represented by the following formula. TIFF0007702806000002.tif984Patent Document 2 describes a salt represented by the following formula. TIFF0007702806000003.tif2489

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Non-Patent Documents

[0004]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention provides a carboxylate that forms a resist pattern with better line edge roughness (LER) than a resist pattern formed by a resist composition containing the above salt.

Means for Solving the Problems

[0006] The present invention includes the following inventions. [1] A carboxylate represented by formula (I). TIFF0007702806000004.tif32164[In formula (I), R 1 and R 2 each independently represents an iodine atom, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms. R 4 , R 5 , R 7 and R 8 each independently represents a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms, and -CH2- contained in the haloalkyl group and the alkyl group may be replaced by -O-, -CO-, -S-, or -SO2-. X 1 and X 2 each independently represents an oxygen atom or a sulfur atom. m1 represents any integer from 1 to 5, and when m1 is 2 or more, the groups in multiple parentheses may be the same as or different from each other. m2 represents any integer from 0 to 5, and when m2 is 2 or more, the groups in multiple parentheses may be the same as or different from each other. m4 represents any integer from 0 to 4, and when m4 is 2 or more, the multiple R 4 may be the same as or different from each other. m5 represents any integer from 0 to 4, and when m5 is 2 or more, the multiple R 5 may be the same as or different from each other. m7 represents any integer from 0 to 4, and when m7 is 2 or more, the multiple R 7 may be the same as or different from each other. m8 represents any integer from 0 to 5, and when m8 is 2 or more, the multiple R 8 may be the same as or different from each other. However, 1 ≦ m1 + m7 ≦ 5 and 0 ≦ m2 + m8 ≦ 5. X 0represents a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. [2]X 1 and X 2 are oxygen atoms, and the carboxylate described in [1]. [3]m1 is 1 or 2, m2 is 0, 1 or 2, and the carboxylate described in [1] or [2]. [4]X 1 and X 2 are bonded to the p-position or m-position with respect to the bonding position of I + and the carboxylate described in any one of [1] to [3]. [5]R 4 or R 5 represents an iodine atom, a fluorine atom, a trifluoromethyl group or a hydroxy group, and the carboxylate described in any one of [1] to [4]. [6]m4 is 2, one of the two Rs 4 is an iodine atom, a fluorine atom or a trifluoromethyl group, and the other is a hydroxy group, and the carboxylate described in any one of [1] to [5]. [7]m2 is 0, m8 is 1, R 8 is a branched alkyl group having 3 or 4 carbon atoms, and the carboxylate described in any one of [1] to [6]. [8]m1 and m2 are each 1 or m1 and m2 are each 2, and the carboxylate described in any one of [1] to [6]. [9]X 0 is an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (provided that -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) or an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent, and the carboxylate described in any one of [1] to [8].

[10] X 0is a carboxylate salt according to any one of [1] to [9], which is an alicyclic hydrocarbon group that may have a fluorine atom or a hydroxy group (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-), or an aromatic hydrocarbon group that may have a halogen atom, a hydroxy group or a perfluoroalkyl group having 1 to 4 carbon atoms.

[11] X 0 is a carboxylate salt according to any one of [1] to

[10] , which is a group represented by formula (aa). TIFF0007702806000005.tif2737[In formula (aa), X a and X b each independently represents -O- or -S-. X 1a represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. X 2a represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. * represents the bonding position to the carbon atom of -COO - .]

[12] A carboxylic acid generator containing the carboxylate salt according to any one of [1] to

[11] .

[13] A resist composition containing the carboxylic acid generator according to

[12] , an acid generator other than the carboxylic acid generator, and a resin having an acid-labile group.

[14] The resist composition according to

[13] , wherein the resin having an acid-labile group contains at least one selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2). TIFF0007702806000006.tif46102[In formula (a1-1) and formula (a1-2), L a1 and L a2 each independently represents -O- or *-O-(CH2) k1-CO-O- represents, k1 represents any integer from 1 to 7, and * represents the bonding position with -CO-. R a4 and R a5 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. m1 represents any integer from 0 to 14. n1 represents any integer from 0 to 10. n1’ represents any integer from 0 to 3.

[15] The resist composition according to

[13] or

[14] , wherein the resin having an acid-labile group contains a structural unit represented by the formula (a2-A). TIFF0007702806000007.tif4653 [In the 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 alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 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 represents a single bond or * -X a51 -(A a52 -X a52 ) nb - represents, and * represents the bond with the carbon atom to which -R a50 is bonded. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52Each independently represents -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents any integer from 0 to 4. When mb is any integer of 2 or more, a plurality of Rs a51 may be the same as or different from each other.

[16] (1) A step of applying the resist composition described in any one of

[13] to

[15] on a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the exposed composition layer, and (5) A step of developing the heated composition layer, which is a method for manufacturing a resist pattern. [Effect of the Invention]

[0007] By using the resist composition using the carboxylate of the present invention, a resist pattern can be manufactured with good line edge roughness (LER). [Mode for Carrying Out the Invention]

[0008] In this specification, the “(meth)acrylic monomer” means “at least one of an acrylic monomer and a methacrylic monomer”. Notations such as “(meth)acrylate” and “(meth)acrylic acid” also have the same meaning. For groups described in this specification that can take both a linear structure and a branched structure, either one is acceptable. “Derived from” or “derived” refers to the fact that the polymerizable C═C bond contained in the molecule becomes a -C-C- group by polymerization. When -CH2- contained in a hydrocarbon group or the like is replaced by -O-, -S-, -CO- or -SO2-, the same examples apply to each group. The “combined group” means a group formed by bonding two or more of the exemplified groups, and the valence of these groups may be appropriately changed depending on the bonding form. “Derived from” or “derived” refers to the fact that the polymerizable C═C bond contained in the molecule becomes a -C-C- group by polymerization. When stereoisomers exist, all stereoisomers are included. In this specification, the "solid content of the resist composition" means the total of the components excluding the solvent (E) described later from the total amount of the resist composition.

[0009] [Carboxylate represented by formula (I)] The present invention relates to a carboxylate represented by formula (I) (hereinafter sometimes referred to as "salt (I)"). Among salts (I), the side having a negative charge may be referred to as "anion (I)", and the side having a positive charge may be referred to as "cation (I)". TIFF0007702806000008.tif32164[In the formula, all symbols have the same meanings as described above respectively.]

[0010] R 1 and R 2 Examples of the C1-C6 fluoroalkyl group of R and R include fluoroalkyl groups such as 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, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, perfluorohexyl group and the like. The number of carbon atoms of the fluoroalkyl group is preferably 1-4, more preferably 1-3. R 4 、R 5 、R 7 and R 8 Examples of the halogen atom of R, R, R and R include fluorine atom, chlorine atom, bromine atom, iodine atom and the like. R 4 、R 5 、R 7 and R 8The C1-C12 haloalkyl group herein represents an alkyl group having 1 to 12 carbon atoms and a halogen atom, and examples thereof include chloromethyl group, bromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, perfluorobutyl, etc. The number of carbon atoms of the haloalkyl group is preferably 1 to 9, more preferably 1 to 6, and still more preferably 1 to 4. R 4 , R 5 , R 7 and R 8 Examples of the C1-C12 alkyl group for R R 4 , R 5 , R 7 and R 8When -CH2- contained in the haloalkyl group or alkyl group represented by is replaced by -O-, -CO-, -S- or -SO2-, the number of carbon atoms before replacement shall be the total number of carbon atoms of the haloalkyl group or the alkyl group. Examples of the replaced group include a hydroxy group (a group in which -CH2- contained in a methyl group is replaced by -O-), a carboxy group (a group in which -CH2-CH2- contained in an ethyl group is replaced by -O-CO-), a thiol group (a group in which -CH2- contained in a methyl group is replaced by -S-), an alkoxy group (a group in which -CH2- at any position contained in an alkyl group is replaced by -O-), an alkylthio group (a group in which -CH2- at any position contained in an alkyl group is replaced by -S-), an alkylsulfonyl group (a group in which -CH2- at any position contained in an alkyl group is replaced by -SO2-), an alkoxycarbonyl group (a group in which -CH2-CH2- at any position contained in an alkyl group is replaced by -O-CO-), an alkylcarbonyl group (a group in which -CH2- at any position contained in an alkyl group is replaced by -CO-), an alkylcarbonyloxy group (a group in which -CH2-CH2- at any position contained in an alkyl group is replaced by -CO-O-), and a group formed by combining two or more of these groups. Examples of the alkoxy group include alkoxy groups having 1 to 11 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, and an undecyloxy group. The number of carbon atoms of the alkoxy group is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3. Examples of the alkylthio group include alkylthio groups having 1 to 12 carbon atoms, such as a methylthio group, an ethylthio group, a propylthio group, and a butylthio group. The number of carbon atoms of the alkylthio group is preferably 1 to 6, and more preferably 1 to 4. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 12 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group and the like. The number of carbon atoms of the alkylsulfonyl group is more preferably 1 to 6, and even more preferably 1 to 4. The alkoxycarbonyl group, alkylcarbonyl group and alkylcarbonyloxy group represent groups in which a carbonyl group or a carbonyloxy group is bonded to the above-described alkyl group or alkoxy group. Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 11 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and the like. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 12 carbon atoms, such as acetyl group, propionyl group and butyryl group and the like. Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having 2 to 11 carbon atoms, such as acetyloxy group, propionyloxy group, butyryloxy group and the like. The number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkylcarbonyl group is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkylcarbonyloxy group is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. It should be noted that the replacement of the haloalkyl group is applied in the same manner as the replacement of the alkyl group. X 1 is preferably an oxygen atom. X 2 is preferably an oxygen atom. X 1 and X 2 The bonding positions of + may be any of the ortho position, meta position and para position with respect to the bonding position of I + . Among them, it is preferably bonded to the para position or meta position with respect to the bonding position of I m1 is preferably 1 or 2. m2 is preferably 0, 1 or 2. m4 is preferably 0, 1, 2 or 4. m5 is preferably 0 or 1. m7 is preferably 0, 1 or 2, more preferably 0 or 1. m8 is preferably 0 or 1. R 4 and R 5 are each independently preferably an iodine atom, a fluorine atom, a hydroxy group, a haloalkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms (wherein -CH2- contained in the haloalkyl group and the alkyl group may be replaced by -O- or -CO-), more preferably an iodine atom, a fluorine atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, still more preferably an iodine atom, a fluorine atom, a hydroxy group or an alkoxy group having 1 to 3 carbon atoms, and even more preferably an iodine atom, a fluorine atom or a hydroxy group. R 7 and R 8 are each independently preferably an iodine atom, a fluorine atom, a hydroxy group, a haloalkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms (wherein -CH2- contained in the haloalkyl group and the alkyl group may be replaced by -O- or -CO-), more preferably an iodine atom, a fluorine atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, still more preferably an iodine atom, a fluorine atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. It is preferable that m1 and m2 are each 1 or that m1 and m2 are each 2. In the embodiment where m2 = 0, m8 is 1, and R 8 is preferably a branched alkyl group having 3 or 4 carbon atoms. In the embodiment where m4 is 2, one of the two R 4 is preferably an iodine atom or a fluorine atom, and the other is preferably a hydroxy group, and the hydroxy group is at I +It is more preferable that it is bonded to the p-position with respect to the bonding position.

[0011] Examples of the cation (I) include the following cations. TIFF0007702806000009.tif153168

[0012] TIFF0007702806000010.tif218168

[0013] TIFF0007702806000011.tif250142

[0014] In formula (I), X 0 Examples of the hydrocarbon group represented by include aliphatic hydrocarbon groups (chain hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups and alicyclic hydrocarbon groups), aromatic hydrocarbon groups, and groups combining these. The -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. Examples of the alkyl group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and nonyl group. The number of carbon atoms of the alkyl group is preferably 1 to 18, more preferably 1 to 12, still more preferably 1 to 9, even more preferably 1 to 6, and even more preferably 1 to 4. Examples of the alkenyl group include ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, octynyl group, isooctynyl group, and nonenyl group. Examples of the alkynyl group include ethynyl group, propynyl group, isopropynyl group, butynyl group, isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octynyl group, and nonynyl group. Examples of groups in which -CH2- contained in the chain hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include a hydroxy group (a group in which -CH2- contained in a methyl group is replaced by -O-), a carboxy group (a group in which -CH2-CH2- contained in an ethyl group is replaced by -O-CO-), a thiol group (a group in which -CH2- contained in a methyl group is replaced by -S-), an alkoxy group (a group in which -CH2- at any position contained in an alkyl group is replaced by -O-), an alkoxycarbonyl group (a group in which -CH2-CH2- at any position contained in an alkyl group is replaced by -O-CO-), an alkylcarbonyl group (a group in which -CH2- at any position contained in an alkyl group is replaced by -CO-), an alkylsulfonyl group (a group in which -CH2- at any position contained in an alkyl group is replaced by -SO2-), an alkylcarbonyloxy group (a group in which -CH2-CH2- at any position contained in an alkyl group is replaced by -CO-O-), an alkylthio group (a group in which -CH2- at any position contained in an alkyl group is replaced by -S-), and the like. Examples of the alkoxy group, the alkoxycarbonyl group, the alkylcarbonyl group, the alkylcarbonyloxy group, the alkylthio group, and the alkylsulfonyl group include the same groups as described above. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 17 carbon atoms, preferably 1 to 11 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. In the case of an alkenyl group or an alkynyl group, the replacement may be any group containing a carbon-carbon double bond or a carbon-carbon triple bond at any position in the examples of the replacement in the above-described alkyl group.

[0015] The alicyclic hydrocarbon group may be monocyclic, polycyclic or spirocyclic, and may be saturated or unsaturated. Examples of the alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclododecyl group, and polycyclic cycloalkyl groups such as norbornyl group and adamantyl group. Examples of the alicyclic hydrocarbon group or the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- specifically include the following. In the following groups, the bonding site can be at any position. TIFF0007702806000012.tif79161 TIFF0007702806000013.tif58160X 0 Examples of the alicyclic hydrocarbon group represented by or the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- are preferably groups represented by formulas (y1) to (y71), more preferably groups represented by any of formulas (y1) to (y20), formula (y26), formula (y27), formula (y30), formula (y31), and formulas (y39) to (y71), and even more preferably groups represented by formula (y3), (y4), formula (y9), formula (y11), formula (y14), formula (y15), formula (y16), formula (y20), formula (y26), formula (y27), formula (y30), formula (y31), formula (y39), formula (y40), formula (y42), formula (y43), and formulas (y49) to (y58), and formulas (y62) to (y71). The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 36, more preferably 3 to 24, even more preferably 3 to 18, still more preferably 3 to 16.

[0016] Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, and binaphthyl group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 36, more preferably 6 to 24, even more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. In the case of a combined group, it may contain groups with different valences (such as alkanediyl group, alkanetriyl group, alkanetetrayl group, cycloalkanediyl group, cycloalkanetriyl group, cycloalkanetetrayl group, etc.) among the above-mentioned groups.

[0017] The combined group means A group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (wherein -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), A group combining a chain hydrocarbon group and an aromatic hydrocarbon group (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), and A group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). In the combination, the alicyclic hydrocarbon group, the chain hydrocarbon group and the aromatic hydrocarbon group may each be combined with two or more kinds. Specifically, as the combined group, An alicyclic hydrocarbon group-chain hydrocarbon group-* such as an adamantylmethylene group, a cyclohexylmethylene group, ((alicyclic hydrocarbon group)2-chain hydrocarbon group-* (wherein -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), A chain hydrocarbon group-alicyclic hydrocarbon group-* such as a methyladamantyl group, a dimethyladamantyl group, ((chain hydrocarbon group)2-alicyclic hydrocarbon group-* (wherein -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), A chain hydrocarbon group-aromatic hydrocarbon group-* such as a tolyl group, a xylyl group (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), A chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-* such as a methylcyclohexylmethylene group, ((chain hydrocarbon group)2-alicyclic hydrocarbon group-chain hydrocarbon group-*, ((chain hydrocarbon group-alicyclic hydrocarbon group)2-chain hydrocarbon group-* (wherein -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), An aromatic hydrocarbon group such as a benzyl group - a chain hydrocarbon group - *(the -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), A chain hydrocarbon group such as a tolylmethyl group - an aromatic hydrocarbon group - a chain hydrocarbon group - *(the -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), A chain hydrocarbon group - an alicyclic hydrocarbon group - a chain hydrocarbon group - an alicyclic hydrocarbon group - * such as a methyladamantylmethyleneadamantyl group, a di(methyladamantylmethylene)adamantyl group, etc., (a chain hydrocarbon group - an alicyclic hydrocarbon group - a chain hydrocarbon group)2 - an alicyclic hydrocarbon group - *, (a chain hydrocarbon group - an alicyclic hydrocarbon group)2 - a chain hydrocarbon group - an alicyclic hydrocarbon group - *, (a chain hydrocarbon group)2 - an alicyclic hydrocarbon group - a chain hydrocarbon group - an alicyclic hydrocarbon group - *(the -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), An alicyclic hydrocarbon group - a chain hydrocarbon group - an alicyclic hydrocarbon group - a chain hydrocarbon group - *, (an alicyclic hydrocarbon group)2 - a chain hydrocarbon group - an alicyclic hydrocarbon group - a chain hydrocarbon group - *, (an alicyclic hydrocarbon group - a chain hydrocarbon group)2 - an alicyclic hydrocarbon group - a chain hydrocarbon group - *, (an alicyclic hydrocarbon group - a chain hydrocarbon group - an alicyclic hydrocarbon group)2 - a chain hydrocarbon group - *(the -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), A chain hydrocarbon group - an alicyclic hydrocarbon group - a chain hydrocarbon group - an alicyclic hydrocarbon group - a chain hydrocarbon group - *, (a chain hydrocarbon group)2 - an alicyclic hydrocarbon group - a chain hydrocarbon group - an alicyclic hydrocarbon group - a chain hydrocarbon group - *, (a chain hydrocarbon group - an alicyclic hydrocarbon group)2 - a chain hydrocarbon group - an alicyclic hydrocarbon group - a chain hydrocarbon group - *, (a chain hydrocarbon group - an alicyclic hydrocarbon group - a chain hydrocarbon group)2 - an alicyclic hydrocarbon group - a chain hydrocarbon group - *, (a chain hydrocarbon group - an alicyclic hydrocarbon group - a chain hydrocarbon group - an alicyclic hydrocarbon group)2 - a chain hydrocarbon group - *(the -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), Examples include the following. Here, * represents the bonding position to the carbon atom of the carbonyl group.

[0018] X 0 When -CH2- contained in the hydrocarbon group represented by is replaced by -O-, -S-, -CO- or -SO2-, the total carbon number of the hydrocarbon group is the carbon number before replacement. Also, when a substituent is bonded to the hydrocarbon group represented by X 0 the total carbon number of the hydrocarbon group is the carbon number before substitution.

[0019] X 0 The hydrocarbon group represented by may have one or more substituents. Examples of the substituent include a halogen atom, a cyano group, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group combining these. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a fluorine atom is preferable. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, etc. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, etc. The alkoxycarbonyl group having 2 to 13 carbon atoms, the alkylcarbonyl group having 2 to 13 carbon atoms, and the alkylcarbonyloxy group having 2 to 13 carbon atoms represent a group in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group and the like. Examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, a butyryl group and the like. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like. Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include the groups shown below. ** represents the bonding position with X 0 and. TIFF0007702806000014.tif17162 Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include aryl groups such as a phenyl group and a naphthyl group. Examples of the combined group include a group formed by combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms, a group formed by combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, a group formed by combining an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the like. Examples of the group formed by combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms include hydroxyalkyl groups having 1 to 12 carbon atoms such as a hydroxymethyl group and a hydroxyethyl group. Examples of the group formed by combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms include aralkyl groups having 7 to 22 carbon atoms such as a benzyl group, and alkylaryl groups having 7 to 22 carbon atoms such as a tolyl group and a xylyl group. Examples of the group formed by combining an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms include a cyclohexylphenyl group and the like.

[0020] X 0 The hydrocarbon group represented by is preferably an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (wherein -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent, More preferably, it is an alicyclic hydrocarbon group which may have a hydroxy group or a fluorine atom (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group), a halogen atom, an aromatic hydrocarbon group which may have a hydroxy group or a C1-C4 perfluoroalkyl group, a group represented by formula (aa) or a group represented by formula (bb), Even more preferably, it is a *-alicyclic hydrocarbon group (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom. * represents the bonding position with the carbon atom of the carbonyl group), a *-alicyclic hydrocarbon group-chain hydrocarbon group (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group. * represents the bonding position with the carbon atom of the carbonyl group), a *-chain hydrocarbon group-alicyclic hydrocarbon group (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the chain hydrocarbon group and the alicyclic hydrocarbon group may have a fluorine atom or a hydroxy group. * represents the bonding position with the carbon atom of -COO - of the carbon atom), a fluorine atom or an aromatic hydrocarbon group which may have a hydroxy group, a group represented by formula (aa) or a group represented by formula (bb), More preferably, it is a polycyclic alicyclic hydrocarbon group (wherein -CH2- contained in the polycyclic alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the polycyclic alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom. * represents the bonding position with the carbon atom of the carbonyl group.), a polycyclic alicyclic hydrocarbon group - a chain hydrocarbon group (wherein -CH2- contained in the polycyclic alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the polycyclic alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group. * represents the bonding position with the carbon atom of the carbonyl group.), a chain hydrocarbon group - a polycyclic alicyclic hydrocarbon group (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and -CH2- contained in the polycyclic alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the chain hydrocarbon group and the polycyclic alicyclic hydrocarbon group may have a fluorine atom or a hydroxy group. * represents the bonding position with the carbon atom of -COO - the carbon atom of).), an aromatic hydrocarbon group which may have a fluorine atom or a hydroxy group, a group represented by the formula (aa) or a group represented by the formula (bb), Particularly preferably, it is an adamantanone group, a hydroxyadamantyl group, a group combining an adamantyl group and an alkyl group (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), a group represented by the formula (Y30F), or a phenyl group having a hydroxy group. Based on the above, the number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 36, more preferably 3 to 24, still more preferably 3 to 18, even more preferably 3 to 16, and even more preferably 3 to 12. The number of carbon atoms in the chain hydrocarbon group is preferably 1 to 18, more preferably 1 to 12, still more preferably 1 to 9, even more preferably 1 to 6, and even more preferably 1 to 4. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 36, more preferably 6 to 24, still more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. TIFF0007702806000015.tif26127[In formula (aa), X a and X b each independently represents -O- or -S-. X 1a represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. X 2a represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. * represents the bonding position with the carbon atom of -COO - . [In formula (bb), L A represents an alkanediyl group having 1 to 6 carbon atoms which may have a fluorine atom, or an aromatic hydrocarbon group having 6 carbon atoms which may have a halogen atom or a perfluoroalkyl group having 1 to 4 carbon atoms. L B represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, and -CH2- contained in the alkanediyl group may be replaced by -O-, -S-, -CO- or -SO2-. R Arepresents a hydrocarbon group having 1 to 36 carbon atoms which may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. * represents the bonding position with the carbon atom of -COO - .

[0021] X a and X b are preferably the same atom, and more preferably both are oxygen atoms.

[0022] X 1a and X 2a Examples of the hydrocarbon group represented by X 1a and X 2a include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group formed by combining two or more of these. Note that these hydrocarbon groups may have substituents. Further, the -CH2- contained in these hydrocarbon groups may be replaced by -O-, -S-, -CO- or -SO2-. Here, the number of carbon atoms of the hydrocarbon group means the number of carbon atoms of the hydrocarbon group having no substituents and no replacements.

[0023] X 1a Examples of the aliphatic hydrocarbon group of X 1a include a chain hydrocarbon group such as an alkanetriyl group, an alicyclic hydrocarbon group, or a group formed by combining these. Specific examples of the alkanetriyl group include a methine group, an ethanetriyl group, a propanetriyl group, a butanetriyl group, a pentanetriyl group, a hexanetriyl group, a heptanetriyl group, an octanetriyl group, a nonanetriyl group, a decanetriyl group, an undecanetriyl group, a dodecanetriyl group, and the like.

[0024] The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclobutanetriyl group, a cyclopentanetriyl group, a cyclohexanetriyl group, a cyclooctanetriyl group, and the like. Examples of the polycyclic alicyclic hydrocarbon group include a norbornanetriyl group, a norbornanetriyl group, an adamantanetriyl group, and the like. Examples of the aromatic hydrocarbon group include a benzene triyl group, a naphthalene triyl group, an anthracene triyl group, and the like. In the case of a combined group, groups having different valences in the above-mentioned groups (such as an alkyl group, an alkane diyl group, an alkane tetrayl group, a cycloalkyl group, a cycloalkane diyl group, a cycloalkane tetrayl group, etc.) may be included.

[0025] X 1a The hydrocarbon group represented by [X] has 1 to 24 carbon atoms and may further have one or more substituents. Examples of the substituent include a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group obtained by combining these. Examples of the halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and a group obtained by combining these are the same as those described above. Among them, a fluorine atom is preferable as the halogen atom.

[0026] X 1a The hydrocarbon group represented by [X] is preferably an alkanetriyl group having 1 to 6 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably an alkanetriyl group having 1 to 6 carbon atoms, a group represented by formula (w1-1) to formula (w1-11), still more preferably a polycyclic hydrocarbon group such as an alkanetriyl group having 1 to 6 carbon atoms, a group represented by formula (w1-1) or a group represented by formula (w1-3), or a monocyclic hydrocarbon group such as a group represented by formula (w1-2) or a group represented by formula (w1-6). TIFF0007702806000016.tif53143[In formula (w1-1) to formula (w1-11), The ring may have a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group combining these. * represents the bonding position.

[0027] X 2a The hydrocarbon group represented by is preferably 2 to 48 in carbon number, more preferably 4 to 48, even more preferably 6 to 44, still more preferably 8 to 40, and yet more preferably 10 to 38.

[0028] X 2a Examples of the substituent that the hydrocarbon group in may have include a halogen atom, a cyano group, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group combining these. Examples of the halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and the group combining these are the same as those described above. X 2a The hydrocarbon group having 1 to 48 carbon atoms represented by may have one substituent or a plurality of substituents.

[0029] X 2a Examples of the hydrocarbon group in include a linear or branched chain hydrocarbon group (e.g., an alkanediyl group, etc.), a monocyclic or polycyclic alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and those combining two or more of these groups may also be used. Specifically, linear alkanediyl groups such as 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; Branched alkanediyl groups such as 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, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; Monocyclic alicyclic hydrocarbon groups that are monocyclic alkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; Polycyclic alicyclic hydrocarbon groups that are polycyclic alkanediyl groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group; Aromatic hydrocarbon groups such as phenylene group, naphthylene group, biphenylene group, anthrylene group, phenanthrylene group, binaphthylene group, etc. can be mentioned. In the case of a combined group, groups with different valences (alkyl group, alkanetriyl group, alkanetetrayl group, cycloalkyl group, cycloalkanetriyl group, cycloalkanetetrayl group, etc.) in the above-mentioned groups may be included. Examples of the combined groups include a group combining an aliphatic hydrocarbon group and an alicyclic hydrocarbon group, a group combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group, a group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group, etc. Specifically, examples include a group in which one or more alicyclic hydrocarbon groups are bonded to an aliphatic hydrocarbon group (e.g., -aliphatic hydrocarbon group-alicyclic hydrocarbon group, -aliphatic hydrocarbon group-(alicyclic hydrocarbon group)2, etc.), a group in which one or more aliphatic hydrocarbon groups are bonded to an alicyclic hydrocarbon group (e.g., -alicyclic hydrocarbon group-aliphatic hydrocarbon group, -alicyclic hydrocarbon group-(aliphatic hydrocarbon group)2, etc.), a group in which one or more alicyclic hydrocarbon groups and aliphatic hydrocarbon groups are bonded to an aliphatic hydrocarbon group (e.g., -aliphatic hydrocarbon group-alicyclic hydrocarbon group-aliphatic hydrocarbon group, -aliphatic hydrocarbon group-(alicyclic hydrocarbon group-aliphatic hydrocarbon group)2, etc.).

[0030] X 2a Examples of the hydrocarbon group in an aliphatic hydrocarbon group having 2 to 18 carbon atoms which may have a substituent (wherein -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or a group combining an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent (wherein -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) is preferred. an aliphatic hydrocarbon group having 4 to 18 carbon atoms which may have a substituent (wherein -CH2- contained in the aliphatic saturated hydrocarbon group may be replaced by -O- or -CO-), or A group formed by combining an optionally substituted linear hydrocarbon group having 1 to 12 carbon atoms (wherein -CH2- contained in the linear hydrocarbon group may be replaced by -O- or -CO-) and an optionally substituted alicyclic hydrocarbon group having 3 to 16 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) is more preferable. An optionally substituted linear hydrocarbon group having 6 to 14 carbon atoms (wherein -CH2- contained in the linear hydrocarbon group may be replaced by -O- or -CO-), or A group formed by combining an optionally substituted linear hydrocarbon group having 1 to 12 carbon atoms (wherein -CH2- contained in the linear hydrocarbon group may be replaced by -O- or -CO-) and an optionally substituted alicyclic hydrocarbon group having 5 to 14 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) is even more preferable.

[0031] Specifically, the hydrocarbon group in X 2a is, An optionally substituted alkanediyl group having 2 to 18 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), An optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), A group composed of an optionally substituted alkanediyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-) and an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or An alkane diyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and an alkyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), and it is preferably a group composed of these, An alkane diyl group having 4 to 18 carbon atoms which may have a substituent (wherein -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-), A group composed of an alkane diyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-) and an alicyclic saturated hydrocarbon group having 3 to 16 carbon atoms which may have a substituent (wherein -CH2- contained in the alicyclic saturated hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or A group composed of an alkane diyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-), an alicyclic saturated hydrocarbon group having 3 to 16 carbon atoms which may have a substituent, and an alkyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), and it is more preferably a group composed of these, An alkane diyl group having 6 to 14 carbon atoms which may have a substituent (wherein -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-), A group composed of an alkane diyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-) and an adamantane diyl group which may have a substituent (wherein -CH2- contained in the adamantane diyl group may be replaced by -O- or -CO-), or An alkane diyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-), an adamantane diyl group which may have a substituent, and an alkyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-). It is more preferably a group consisting of these.

[0032] Specifically, X 2a is preferably a group represented by formula (X 2 -1), a group represented by formula (X 2 -2), a group represented by formula (X 2 -3), or a group represented by formula (X 2 -4). TIFF0007702806000017.tif34157 [In the formula, R 1x 、R 2x 、R 3x 、R 4x 、R 5x and R 6x each independently represents an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by combining two or more of these groups. -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO-, or -SO2-, and the alkyl group and the alicyclic hydrocarbon group may have a substituent. * represents the bonding position with X a and X b .] The combined group may be one formed by combining one alkyl group and one alicyclic hydrocarbon group as described above, or a group formed by combining two or more of either or both. In this case, the carbon number of the combined group is 39 or less, preferably 37 or less.

[0033] Among them, R 1x 、R 2x 、R 3x 、R 4x 、R 5x and R 6xExamples include an alkyl group having 1 to 6 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-, and the alkyl group may have a substituent), an alicyclic hydrocarbon group having 5 to 12 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the alicyclic hydrocarbon group may have a substituent), or a group formed by combining an alkyl group having 1 to 6 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 5 to 12 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) (the group may have a substituent). Preferably, it is a methoxy group, an adamantyl group (wherein -CH2- contained in the adamantyl group may be replaced by -O- or -CO-, and the adamantyl group may have a substituent), or a group formed by combining an alkyl group having 1 to 6 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-) and an adamantyl group (the group may have a substituent). More preferably, it is such a group.

[0034] In formula (bb), L A and L B Examples of the alkanediyl group having 1 to 6 carbon atoms include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group; and branched alkanediyl groups such as a propane-1,2-diyl group, a 1-methylpropane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a 1-methylbutane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. The number of carbon atoms of the alkanediyl group is preferably 1 to 4, and more preferably 1 to 3. Examples of the alkanediyl group which may have a fluorine atom include perfluoroalkanediyl groups such as a difluoromethylene group, a perfluoroethylene group, a perfluoropropanediyl group, a perfluorobutanediyl group, and a perfluoropentanediyl group. L BWhen -CH2- contained in the alkanediyl group is replaced by -O-, -S-, -CO- or -SO2-, the carbon number before replacement is defined as the total carbon number of the alkanediyl group. The alkanediyl group may have a hydroxy group (a group in which -CH2- contained in the methyl group is replaced by -O-), a carboxy group (a group in which -CH2-CH2- contained in the ethyl group is replaced by -O-CO-), a thiol group (a group in which -CH2- contained in the methyl group is replaced by -S-), an alkoxy group (a group in which -CH2- at any position contained in the alkyl group is replaced by -O-), an alkoxycarbonyl group (a group in which -CH2-CH2- at any position contained in the alkyl group is replaced by -O-CO-), an alkylcarbonyl group (a group in which -CH2- at any position contained in the alkyl group is replaced by -CO-), an alkylcarbonyloxy group (a group in which -CH2-CH2- at any position contained in the alkyl group is replaced by -CO-O-), an alkylthio group (a group in which -CH2- at any position contained in the alkyl group is replaced by -S-), an alkylsulfonyl group (a group in which -CH2- at any position contained in the alkyl group is replaced by -SO2-), an alkanediyl-oxy group (a group in which -CH2- at any position contained in the alkanediyl group is replaced by -O-), an alkanediylthio group (a group in which -CH2- at any position contained in the alkanediyl group is replaced by -S-), an alkanediylsulfonyl group (a group in which -CH2- at any position contained in the alkanediyl group is replaced by -SO2-), an alkanediyl-oxycarbonyl group (a group in which -CH2-CH2- at any position contained in the alkanediyl group is replaced by -O-CO-), an alkanediylcarbonyl group (a group in which -CH2- at any position contained in the alkanediyl group is replaced by -CO-), or an alkanediylcarbonyloxy group (a group in which -CH2-CH2- at any position contained in the alkanediyl group is replaced by -CO-O-). Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alkylthio group, and alkylsulfonyl group are the same as those described above. Examples of the alkanediyl oxy group include a methylene oxy group, an ethylene oxy group, a propanediyl oxy group, a butanediyl oxy group, a pentanediyl oxy group, and the like. Examples of the alkanediyl thio group include a methylene thio group, an ethylene thio group, a propanediyl thio group, a butanediyl thio group, a pentanediyl thio group, and the like. Examples of the alkanediyl sulfonyl group include a methylene sulfonyl group, an ethylene sulfonyl group, a propanediyl sulfonyl group, a butanediyl sulfonyl group, a pentanediyl sulfonyl group, and the like. Examples of the alkanediyl oxycarbonyl group include a methylene oxycarbonyl group, an ethylene oxycarbonyl group, a propanediyl oxycarbonyl group, a butanediyl oxycarbonyl group, and the like. Examples of the alkanediyl carbonyl group include a methylene carbonyl group, an ethylene carbonyl group, a propanediyl carbonyl group, a butanediyl carbonyl group, a pentanediyl carbonyl group, and the like. Examples of the alkanediyl carbonyloxy group include a methylene carbonyloxy group, an ethylene carbonyloxy group, a propanediyl carbonyloxy group, a butanediyl carbonyloxy group, and the like. L A is preferably an alkanediyl group having 1 to 4 carbon atoms which may have a fluorine atom, and more preferably an alkanediyl group having 1 to 3 carbon atoms having a fluorine atom. L B is preferably a single bond or an alkanediyl group having 1 to 3 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), and more preferably a single bond, a methylene group or an ethylene group.

[0035] R A Examples of the hydrocarbon group in R include an aliphatic hydrocarbon group (a chain hydrocarbon group such as an alkyl group, an alkenyl group, an alkynyl group, and an alicyclic hydrocarbon group), an aromatic hydrocarbon group, and a group formed by combining these. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and the like. The number of carbon atoms of the alkyl group is preferably 1 to 18, more preferably 1 to 12, still more preferably 1 to 9, even more preferably 1 to 6, and even more preferably 1 to 4. Examples of the alkenyl group include ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, octynyl group, isooctynyl group, nonenyl group. Examples of the alkynyl group include ethynyl group, propynyl group, isopropynyl group, butynyl group, isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octynyl group, nonynyl group and the like. Examples of the group in which -CH2- contained in the chain hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include hydroxy group, carboxy group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alkylthio group, alkylsulfonyl group and the like. Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group and alkylthio group include, for example, an alkoxy group having 1 to 17 carbon atoms, an alkoxycarbonyl group having 2 to 17 carbon atoms, an alkylcarbonyl group having 2 to 18 carbon atoms, an alkylcarbonyloxy group having 2 to 17 carbon atoms, an alkylthio group having 1 to 17 carbon atoms and an alkylsulfonyl group having 1 to 17 carbon atoms, and groups similar to the above-described groups. The alicyclic hydrocarbon group may be monocyclic, polycyclic or spirocyclic, and may be either saturated or unsaturated. Examples of the monocyclic alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclododecyl group and the like. Examples of the polycyclic alicyclic hydrocarbon group include polycyclic cycloalkyl groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the like. As the alicyclic hydrocarbon group and the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2-, specifically, groups represented by the above formulas (y1) to (y71) and the like can be mentioned. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 36, more preferably 3 to 24, still more preferably 3 to 18, even more preferably 3 to 16, and even more preferably 3 to 12. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, binaphthyl group and the like. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 36, more preferably 6 to 24, still more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. In the case of a combined group, groups having different valences (alkanediyl group, alkanetriyl group, cycloalkanediyl group, cycloalkanetriyl group, etc.) may be included in the above-mentioned groups. Examples of the group formed by combination include a group combining an aromatic hydrocarbon group and a chain hydrocarbon group (for example, aromatic hydrocarbon group - alkanediyl group - *, alkyl group - aromatic hydrocarbon group - *), a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (for example, alicyclic hydrocarbon group - alkanediyl group - *, alkyl group - alicyclic hydrocarbon group - *), and a group combining an aromatic hydrocarbon group and an alicyclic hydrocarbon group (for example, aromatic hydrocarbon group - alicyclic hydrocarbon group - *, alicyclic hydrocarbon group - aromatic hydrocarbon group - *). * represents a bonding site. Examples of the aromatic hydrocarbon group-alkanediyl group-* include aralkyl groups such as benzyl group and phenethyl group. Examples of the alkyl group-aromatic hydrocarbon group-* include tolyl group, xylyl group, cumenyl group and the like. Examples of the alicyclic hydrocarbon group-alkanediyl group-* include cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1-yl)-1-methylethyl and the like. Examples of the alkyl group-alicyclic hydrocarbon group-* include cycloalkyl groups having an alkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, 2-alkyladamantan-2-yl group and the like. Examples of the aromatic hydrocarbon group-alicyclic hydrocarbon group-* include phenyladamantyl group and the like. Examples of the alicyclic hydrocarbon group-aromatic hydrocarbon group-* include adamantylphenyl group and the like. In the combination, two or more alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined with each other. Also, any group may be bonded to L B It may be. Examples of the group in which -CH2- contained in the hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include, in addition to the groups described above, cycloalkoxy group, cycloalkylalkoxy group, alkoxycarbonyloxy group, aromatic hydrocarbon group-carbonyloxy group, and groups combined with two or more of these groups. Examples of the cycloalkoxy group include cycloalkoxy groups having 3 to 17 carbon atoms, such as a cyclohexyloxy group. Examples of the cycloalkylalkoxy group include cycloalkylalkoxy groups having 4 to 17 carbon atoms, such as a cyclohexylmethoxy group. Examples of the alkoxycarbonyloxy group include alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as a butoxycarbonyloxy group. Examples of the aromatic hydrocarbon group-carbonyl-oxy group include aromatic hydrocarbon group-carbonyl-oxy groups having 7 to 17 carbon atoms, such as a benzoyloxy group. When -CH2- contained in the hydrocarbon group is replaced by -O-, -S-, -SO2- or -CO-, the total number of carbon atoms before replacement is defined as the total number of carbon atoms of the hydrocarbon group. The number of such replacements may be one or two or more.

[0036] R A Examples of the substituent that the hydrocarbon group of R may have include a halogen atom, a cyano group, and an alkyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O-, -S-, -CO- or -SO2-). Examples of the halogen atom include the same groups as those described above. Examples of the alkyl group having 1 to 12 carbon atoms include the same groups as those described above. Examples of the group in which -CH2- contained in the alkyl group is replaced by -O- or -CO- include a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, and an alkylcarbonyloxy group. Examples of the alkoxy group, the alkoxycarbonyl group, the alkylcarbonyl group, and the alkylcarbonyloxy group include an alkoxy group having 1 to 11 carbon atoms, an alkoxycarbonyl group having 2 to 11 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, and an alkylcarbonyloxy group having 2 to 11 carbon atoms, such as the same groups as those described above. R A The hydrocarbon group in R may have one substituent or a plurality of substituents.

[0037] R A As the hydrocarbon group in, an alkyl group having 1 to 12 carbon atoms which may have a substituent (provided that -CH2- contained in the alkyl group may be replaced by -O-, -S-, -CO- or -SO2-), or a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) is preferable, and a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 6 carbon atoms (provided that -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) is preferable.

[0038] Examples of the cyclic hydrocarbon group include cyclic hydrocarbon groups such as monocyclic or polycyclic alicyclic hydrocarbon groups having 3 to 18 carbon atoms and aromatic hydrocarbon groups having 6 to 18 carbon atoms, or groups obtained by combining these. Examples of the alicyclic hydrocarbon group, aromatic hydrocarbon group, and combined group are the same as those described above. In the combination, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may each be combined with two or more kinds. Also, any group may be bonded to L B and may be.

[0039] The cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon group may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 6 carbon atoms, and -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms (and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms, It is more preferable that it is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-). As the alicyclic hydrocarbon group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, the following groups (the bonding site is at an arbitrary position) are preferable, and as the aromatic hydrocarbon group, a phenyl group and a naphthyl group are preferable. TIFF0007702806000018.tif1687

[0040] Examples of the anion (I) include carboxylic acid anions described below. TIFF0007702806000019.tif140162

[0041] TIFF0007702806000020.tif78134

[0042] TIFF0007702806000021.tif167142

[0043] TIFF0007702806000022.tif79145

[0044] TIFF0007702806000023.tif155143

[0045] TIFF0007702806000024.tif218160

[0046] TIFF0007702806000025.tif119162 TIFF0007702806000026.tif110153

[0047] Specific examples of the carboxylate (I) include salts obtained by arbitrarily combining the above-mentioned cations and anions. Specific examples of the salt (I) are shown in the following table. In the following table, each symbol represents the symbol attached to the structure representing the above-mentioned anion or cation, and "~" indicates that each of the carboxylate (I) and the anion (I) corresponds. For example, the carboxylate (I-1) is a salt composed of the anion represented by the formula (I-a-1) and the cation represented by the formula (I-c-1), the carboxylate (I-2) is a salt composed of the anion represented by the formula (I-a-2) and the cation represented by the formula (I-c-1), and the carboxylate (I-96) is a salt composed of the anion represented by the formula (I-a-1) and the cation represented by the formula (I-c-2). TIFF0007702806000027.tif2697 [Table 1]

[0048] Among them, as the carboxylate (I), a salt formed by combining an anion represented by any one of the formulas (I-a-1) to (I-a-5), (I-a-10) to (I-a-21), and (I-a-57) to (I-a-66) with a cation represented by any one of the formulas (I-c-1) to (I-c-40) is preferred. Specifically, carboxylate (I-1) to carboxylate (I-5), carboxylate (I-10) to carboxylate (I-21), carboxylate (I-57) to carboxylate (I-66), carboxylate (I-96) to carboxylate (I-100), carboxylate (I-105) to carboxylate (I-116), carboxylate (I-152) to carboxylate (I-161), carboxylate (I-191) to carboxylate (I-195), carboxylate (I-200) to carboxylate (I-211), carboxylate (I-247) to carboxylate (I-256), carboxylate (I-286) to carboxylate (I-290), carboxylate (I-295) to carboxylate (I-306), carboxylate (I-342) to carboxylate (I-351), carboxylate (I-381) to carboxylate (I-385), carboxylate (I-390) to carboxylate (I-401), carboxylate (I-437) to carboxylate (I-446), carboxylate (I-476) to carboxylate (I-480), carboxylate (I-485) to carboxylate (I-496), carboxylate (I-532) to carboxylate (I-541), carboxylate (I-571) to carboxylate (I-575), carboxylate (I-580) to carboxylate (I-591), carboxylate (I-627) to carboxylate (I-636), carboxylate (I-666) to carboxylate (I-670), carboxylate (I-675) to carboxylate (I-686), carboxylate (I-722) to carboxylate (I-731), carboxylate (I-761) to carboxylate (I-765), carboxylate (I-770) to carboxylate (I-781), carboxylate (I-817) to carboxylate (I-826), carboxylate (I-856) to carboxylate (I-860), carboxylate (I-865) to carboxylate (I-876), carboxylate (I-912) to carboxylate (I-921), carboxylate (I-951) to carboxylate (I-955), carboxylate (I-960) to carboxylate (I-971), carboxylate (I-1007) to carboxylate (I-1016),Carboxylate (I-1046) to Carboxylate (I-1050), Carboxylate (I-1055) to Carboxylate (I-1066), Carboxylate (I-1102) to Carboxylate (I-1111), Carboxylate (I-1141) to Carboxylate (I-1145), Carboxylate (I-1150) to Carboxylate (I-1161), Carboxylate (I-1197) to Carboxylate (I-1206), Carboxylate (I-1236) to Carboxylate (I-1240), Carboxylate (I-1245) to Carboxylate (I-1256), Carboxylate (I-1292) to Carboxylate (I-1301), Carboxylate (I-1331) to Carboxylate (I-1335), Carboxylate (I-1340) to Carboxylate (I-1351), Carboxylate (I-1387) to Carboxylate (I-1396), Carboxylate (I-1426) to Carboxylate (I-1430), Carboxylate (I-1435) to Carboxylate (I-1446), Carboxylate (I-1482) to Carboxylate (I-1491), Carboxylate (I-1521) to Carboxylate (I-1525), Carboxylate (I-1530) to Carboxylate (I-1541), Carboxylate (I-1577) to Carboxylate (I-1586), Carboxylate (I-1616) to Carboxylate (I-1620), Carboxylate (I-1625) to Carboxylate (I-1636), Carboxylate (I-1672) to Carboxylate (I-1681), Carboxylate (I-1711) to Carboxylate (I-1715), Carboxylate (I-1720) to Carboxylate (I-1731), Carboxylate (I-1767) to Carboxylate (I-1776), Carboxylate (I-1806) to Carboxylate (I-1810), Carboxylate (I-1815) to Carboxylate (I-1826), Carboxylate (I-1862) to Carboxylate (I-1871), Carboxylate (I-1901) to Carboxylate (I-1905), Carboxylate (I-1910) to Carboxylate (I-1921), Carboxylate (I-1957) to Carboxylate (I-1966), Carboxylate (I-1996) to Carboxylate (I-2000), Carboxylate (I-2005) to Carboxylate (I-2016), Carboxylate (I-2052) to Carboxylate (I-2061), Carboxylate (I-2091) to Carboxylate (I-2095), Carboxylate (I-2100) to Carboxylate (I-2111)Carboxylate (I-2147) to Carboxylate (I-2156), Carboxylate (I-2186) to Carboxylate (I-2190), Carboxylate (I-2195) to Carboxylate (I-2206), Carboxylate (I-2242) to Carboxylate (I-2251), Carboxylate (I-2281) to Carboxylate (I-2285), Carboxylate (I-2290) to Carboxylate (I-2301), Carboxylate (I-2337) to Carboxylate (I-2346), Carboxylate (I-2376) to Carboxylate (I-2380), Carboxylate (I-2385) to Carboxylate (I-2396), Carboxylate (I-2432) to Carboxylate (I-2441), Carboxylate (I-2471) to Carboxylate (I-2475), Carboxylate (I-2480) to Carboxylate (I-2491), Carboxylate (I-2527) to Carboxylate (I-2536), Carboxylate (I-2566) to Carboxylate (I-2570), Carboxylate (I-2575) to Carboxylate (I-2586), Carboxylate (I-2622) to Carboxylate (I-2631), Carboxylate (I-2661) to Carboxylate (I-2665), Carboxylate (I-2670) to Carboxylate (I-2681), Carboxylate (I-2717) to Carboxylate (I-2726), Carboxylate (I-2756) to Carboxylate (I-2760), Carboxylate (I-2765) to Carboxylate (I-2776), Carboxylate (I-2812) to Carboxylate (I-2821), Carboxylate (I-2851) to Carboxylate (I-2855), Carboxylate (I-2860) to Carboxylate (I-2871), Carboxylate (I-2907) to Carboxylate (I-2916), Carboxylate (I-2946) to Carboxylate (I-2950), Carboxylate (I-2955) to Carboxylate (I-2966), Carboxylate (I-3002) to Carboxylate (I-3011), Carboxylate (I-3041) to Carboxylate (I-3045), Carboxylate (I-3050) to Carboxylate (I-3061), Carboxylate (I-3097) to Carboxylate (I-3106), Carboxylate (I-3136) to Carboxylate (I-3140), Carboxylate (I-3145) to Carboxylate (I-3156), Carboxylate (I-3192) to Carboxylate (I-3201), Carboxylate (I-3231) to Carboxylate (I-3235)Carboxylate salts (I-3240) to carboxylate salts (I-3251), carboxylate salts (I-3287) to carboxylate salts (I-3296), carboxylate salts (I-3326) to carboxylate salts (I-3330), carboxylate salts (I-3335) to carboxylate salts (I-3346), carboxylate salts (I-3382) to carboxylate salts (I-3391), carboxylate salts (I-3421) to carboxylate salts (I-3425), carboxylate salts (I-3430) to carboxylate salts (I-3441), carboxylate salts (I-3477) to carboxylate salts (I-3486), carboxylate salts (I-3516) to carboxylate salts (I-3520), carboxylate salts (I-3525) to carboxylate salts (I-3536), carboxylate salts (I-3572) to carboxylate salts (I-3581), carboxylate salts (I-3611) to carboxylate salts (I-3615), carboxylate salts (I-3620) to carboxylate salts (I-3631), carboxylate salts (I-3667) to carboxylate salts (I-3676), carboxylate salts (I-3706) to carboxylate salts (I-3710), carboxylate salts (I-3715) to carboxylate salts (I-3726), carboxylate salts (I-3762) to carboxylate salts (I-3771), carboxylate salts (I-3801) to carboxylate salts (I-3805), carboxylate salts (I-3810) to carboxylate salts (I-3821), carboxylate salts (I-3857) to carboxylate salts (I-3866) are preferred.

[0049] <Method for producing salt (I)> Salt (I) can be produced by reacting a salt represented by formula (I-a) and a salt represented by formula (I-b) in a solvent. TIFF0007702806000029.tif63160[wherein all the symbols have the same meanings as described above. R A 、R B and R C each independently represents a hydrocarbon group having 1 to 12 carbon atoms, or R A 、R B and R C may combine together to form an aromatic ring. R D represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.] Examples of the solvent in this reaction include chloroform, acetonitrile, ion-exchanged water, etc. The reaction temperature is usually 15°C to 80°C, and the reaction time is usually 0.5 to 24 hours.

[0050] The salt represented by formula (I-b) can be synthesized with reference to the methods described in JP-A-2011-39502 and JP-A-2014-88367, and examples thereof include the salts represented below. TIFF0007702806000030.tif133163

[0051] The salt represented by formula (I-a) can be produced by reacting the salt represented by formula (I-c), the compound represented by formula (I-d1), and the compound represented by formula (I-d2) in a solvent in the presence of potassium carbonate. TIFF0007702806000031.tif84142[In the formula, all the symbols have the same meanings as described above.] Examples of the solvent include chloroform, monochlorobenzene, acetonitrile, water, etc. The reaction temperature is usually 15°C to 100°C, and the reaction time is usually 0.5 to 24 hours.

[0052] Examples of the salt represented by formula (I-c) include the salts represented by the following formula, and they can be easily obtained from the market. TIFF0007702806000032.tif46162

[0053] Examples of the compound represented by formula (I-d1) and the compound represented by formula (I-d2) include the compounds represented below, and they can be easily obtained from the market. TIFF0007702806000033.tif41146

[0054] The salt represented by formula (I-a) can be produced by reacting the salt represented by formula (I-e), the compound represented by formula (I-f1), and the compound represented by formula (I-f2) in a solvent in the presence of a base. TIFF0007702806000034.tif87140[In the formula, all the symbols have the same meanings as described above.] Examples of the base include potassium hydroxide and sodium hydride. Examples of the solvent include chloroform, monochlorobenzene, acetonitrile, and water. The reaction temperature is usually 15°C to 100°C, and the reaction time is usually 0.5 to 24 hours.

[0055] Examples of the salt represented by formula (I-e) include salts represented by the following formula, and they can be easily obtained from the market. TIFF0007702806000035.tif1776

[0056] Examples of the compound represented by formula (I-f1) and the compound represented by formula (I-f2) include compounds represented below, and they can be easily obtained from the market. TIFF0007702806000036.tif20164

[0057] [Carboxylic acid generator] The carboxylic acid generator of the present invention is an acid generator containing carboxylate (I). The carboxylate (I) of the present invention can act as an acid generator in the resist composition. When carboxylate (I) is used as the acid generator in the resist composition, the acid generator may contain only one kind or two or more kinds of carboxylates (I). In addition, as described later, the carboxylic acid generator of the present invention may further contain an acid generator known in the resist field other than carboxylate (I) (hereinafter sometimes referred to as "acid generator (B)") and / or a carboxylic acid generator known in the resist field other than carboxylate (I). The acid generator (B) may be used alone or in combination of two or more. When the carboxylic acid generator of the present invention contains an acid generator (B) or the like, the ratio of the contents of the carboxylate (I) and the acid generator (B) or the like (mass ratio; carboxylate (I): acid generator (B)) is usually 1:99 to 100:0, preferably 1:99 to 99:1, more preferably 2:98 to 98:2, and still more preferably 5:95 to 95:5.

[0058] 〔Resist composition〕 The resist composition contains a carboxylic acid generator containing the carboxylate (I) of the present invention, an acid generator (B) other than the carboxylate (I), and a resin having an acid-labile group (hereinafter sometimes referred to as "resin (A)"). Here, the "acid-labile group" means a group having a leaving group, and when contacted with an acid, the leaving group leaves to form a hydrophilic group (for example, a hydroxy group or a carboxy group). The resist composition preferably further contains a quencher (hereinafter sometimes referred to as "quencher (C)") and / or a solvent (hereinafter sometimes referred to as "solvent (E)").

[0059] <Acid generator (B)> Either a nonionic or ionic acid generator (B) may be used. Examples of nonionic acid generators include sulfonate esters (such as 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxy ketone, diazonaphthoquinone 4-sulfonate), sulfones (such as disulfone, ketosulfone, sulfonyldiazomethane), etc. Representative examples of ionic acid generators include onium salts containing an onium cation (such as diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). Examples of anions of onium salts include sulfonic acid anions, sulfonylimide anions, sulfonylmethide anions, etc.

[0060] As the acid generator (B), compounds that generate an acid upon irradiation, as described in JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029, US Patent No. 3,779,778, US Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc., can be used. Further, compounds produced by known methods may also be used. The acid generator (B) may be used in combination of two or more kinds.

[0061] The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a salt represented by the formula (B1) (hereinafter sometimes referred to as "acid generator (B1)"). TIFF0007702806000037.tif2962[In the formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-. Z + represents an organic cation.]

[0062] Q b1 and Q b2Examples of the perfluoroalkyl group represented by [compound 1] include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. Q b1 and Q b2 are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably both are fluorine atoms.

[0063] L b1 Examples of the divalent saturated hydrocarbon group in [compound 2] include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and a group formed by combining two or more of these groups may also be used. Specifically, linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, and a heptadecane-1,17-diyl group; branched alkanediyl groups such as an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group; monocyclic divalent alicyclic saturated hydrocarbon groups that are cycloalkanediyl groups such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, and a cyclooctane-1,5-diyl group; Examples thereof include polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, and the like.

[0064] L b1 Examples of the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced by -O- or -CO- include groups represented by any of formula (b1-1) to formula (b1-3). In the groups represented by formula (b1-1) to formula (b1-3) and the groups represented by formula (b1-4) to formula (b1-11) which are specific examples thereof, * and ** represent bonding positions, and * represents the bonding position with -Y.

[0065] TIFF0007702806000038.tif26117[In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a fluorine atom. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. However, b2 the total number of carbon atoms of L b3 and L In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a fluorine atom. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. However, b4 the total number of carbon atoms of L b5The total number of carbon atoms with [the relevant group] 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, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, the total number of carbon atoms of L b6 and L b7 is 23 or less.

[0066] In the groups represented by formula (b1-1) to formula (b1-3), when -CH2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-, the number of carbon atoms before replacement is taken as the number of carbon atoms of the saturated hydrocarbon group. Examples of the divalent saturated hydrocarbon group include the same ones as the divalent saturated hydrocarbon group of L b1 .

[0067] 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, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms. 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, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b7is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-.

[0068] L b1 As the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by b1 is replaced with -O- or -CO-, the group represented by formula (b1-1) or formula (b1-3) is preferable.

[0069] Examples of the group represented by formula (b1-1) include the groups represented by formulas (b1-4) to (b1-8), respectively. TIFF0007702806000039.tif48120[In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, b9 L b10 and the total carbon number of L b10 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, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, b11 L b12The total carbon number 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, and -CH2- contained in the divalent saturated 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, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. However, the total carbon number of L b13 to L b15 is 19 or less. In formula (b1-8), L b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group 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, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. However, the total carbon number of L b16 to L b18 is 19 or less.

[0070] 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 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 b12is 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 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 a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0071] Examples of the group represented by the formula (b1-3) include the groups represented by the formulas (b1-9) to (b1-11). TIFF0007702806000040.tif23140[In the formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon 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, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, the total carbon number of L b19 and L b20 is 23 or less. In the formula (b1-10), L b21represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. 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, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms, hydroxy groups or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms contained in the alkylcarbonyloxy group may be substituted with hydroxy groups. 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, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. 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, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms, hydroxy groups or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms contained in the alkylcarbonyloxy group may be substituted with hydroxy groups. However, L b24 、L b25 and L b26 The total number of carbon atoms is 21 or less.]

[0072] In the group represented by formula (b1-9) to the group represented by formula (b1-11), when the hydrogen atoms contained in the saturated hydrocarbon group are substituted with alkylcarbonyloxy groups, the number of carbon atoms before substitution is taken as the number of carbon atoms of the saturated hydrocarbon group.

[0073] Examples of the alkyloxycarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, and an adamantylcarbonyloxy group.

[0074] Examples of the group represented by formula (b1-4) include the following. TIFF0007702806000041.tif16154

[0075] Examples of the group represented by formula (b1-5) include the following. TIFF0007702806000042.tif68152

[0076] Examples of the group represented by formula (b1-6) include the following. TIFF0007702806000043.tif32164

[0077] Examples of the group represented by formula (b1-7) include the following. TIFF0007702806000044.tif57146

[0078] Examples of the group represented by formula (b1-8) include the following. TIFF0007702806000045.tif23150

[0079] Examples of the group represented by formula (b1-2) include the following. TIFF0007702806000046.tif31161

[0080] Examples of the group represented by formula (b1-9) include the following. TIFF0007702806000047.tif44137

[0081] Examples of the group represented by formula (b1-10) include the following. TIFF0007702806000048.tif92165

[0082] Examples of the group represented by formula (b1-11) include the following. TIFF0007702806000049.tif84164

[0083] Examples of the alicyclic hydrocarbon group represented by Y include the groups represented by formula (Y1) to formula (Y11), formula (Y36) to formula (Y38). When -CH2- contained in the alicyclic hydrocarbon group represented by Y is replaced by -O-, -SO2- or -CO-, the number thereof may be one or two or more. Examples of such groups include the groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43). TIFF0007702806000050.tif84169

[0084] The alicyclic hydrocarbon group represented by Y is preferably a group represented by any one of formula (Y1) to formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) to formula (Y43), more preferably a group represented by formula (Y11), formula (Y15), formula (Y16), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43), and even more preferably a group represented by formula (Y11), formula (Y15), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43). When the alicyclic hydrocarbon group represented by Y is a spiro ring such as formula (Y28) to formula (Y35), formula (Y39) to formula (Y40), formula (Y42) or formula (Y43), etc., the alkanediyl group between the two oxygen atoms preferably has one or more fluorine atoms. Further, among the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom is preferably not substituted with a fluorine atom.

[0085] Examples of the substituent of the methyl group represented by Y include a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group, -(CH2) ja -CO-O-R b1 group or -(CH2) ja -O-CO-R b1 group (wherein R b1 represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. ja represents any integer from 0 to 4. The -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-, and the hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced by a hydroxy group or a fluorine atom.). etc. are mentioned. Examples of the substituent of the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 16 carbon atoms which may be substituted by a hydroxy group (the -CH2- contained in the alkyl group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, a glycidyloxy group, -(CH2) ja -CO-O-R b1 group or -(CH2) ja -O-CO-R b1 group (wherein R b1 represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. ja represents any integer from 0 to 4. The -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-, and the hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced by a hydroxy group or a fluorine atom.). etc. are mentioned.

[0086] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an adamantyl group, and the like. The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples thereof include a methylcyclohexyl group and a dimethylcyclohexyl group. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 12, more preferably 3 to 10. Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples thereof include an aromatic hydrocarbon group having a chain hydrocarbon group having 1 to 18 carbon atoms (a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a p-methylphenyl group, a p-ethylphenyl group, a p-tert-butylphenyl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.), and an aromatic hydrocarbon group having an alicyclic hydrocarbon group having 3 to 18 carbon atoms (a p-cyclohexylphenyl group, a p-adamantylphenyl group, etc.). The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 14, more preferably 6 to 10. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and the like. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkyl group substituted with a hydroxy group include hydroxyalkyl groups such as a hydroxymethyl group and a hydroxyethyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group. Examples of groups in which -CH2- contained in an alkyl group is replaced by -O-, -SO2-, -CO- or the like include an alkoxy group, an alkylsulfonyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, or a group formed by combining these groups. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, dodecyloxy and the like. The number of carbon atoms in the alkoxy group is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 4. Examples of alkylsulfonyl groups include methylsulfonyl, ethylsulfonyl, propylsulfonyl and the like. The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 4. Examples of alkoxycarbonyl groups include, for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl and the like. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of alkylcarbonyl groups include, for example, acetyl, propionyl, butyryl and the like. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of alkylcarbonyloxy groups include, for example, acetyloxy, propionyloxy, butyryloxy and the like. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the combined group include a group formed by combining an alkoxy group and an alkyl group, a group formed by combining an alkoxy group and an alkoxy group, a group formed by combining an alkoxy group and an alkylcarbonyl group, a group formed by combining an alkoxy group and an alkylcarbonyloxy group, and the like. Examples of the group combining an alkoxy group and an alkyl group include alkoxyalkyl groups such as methoxymethyl group, methoxyethyl group, ethoxyethyl group, ethoxy methyl group, etc. The number of carbon atoms of the alkoxyalkyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the group combining an alkoxy group and an alkoxy group include alkoxyalkoxy groups such as methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, ethoxyethoxy group, etc. The number of carbon atoms of the alkoxyalkoxy group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the group combining an alkoxy group and an alkylcarbonyl group include alkoxyalkylcarbonyl groups such as methoxyacetyl group, methoxypropionyl group, ethoxyacetyl group, ethoxypropionyl group, etc. The number of carbon atoms of the alkoxyalkylcarbonyl group is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. Examples of the group combining an alkoxy group and an alkylcarbonyloxy group include alkoxyalkylcarbonyloxy groups such as methoxyacetyloxy group, methoxypropionyloxy group, ethoxyacetyloxy group, ethoxypropionyloxy group, etc. The number of carbon atoms of the alkoxyalkylcarbonyloxy group is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. Examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -SO2- or -CO- etc. include the groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43), etc.

[0087] Examples of Y include the following. TIFF0007702806000051.tif86165

[0088] TIFF0007702806000052.tif76161

[0089] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, still more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and still more preferably an adamantyl group which may have a substituent; and -CH2- constituting the alicyclic hydrocarbon group or adamantyl group may be replaced by -CO-, -SO2- or -CO-. Specifically, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or a group represented by formula (Y42), formula (Y100) to formula (Y114).

[0090] As the anion in the salt represented by formula (B1), anions represented by formula (B1-A-1) to formula (B1-A-59) [hereinafter sometimes referred to as "anion (B1-A-1)" etc. according to the formula number] are preferable, and an anion represented by any of formula (B1-A-1) to formula (B1-A-4), formula (B1-A-9), formula (B1-A-10), formula (B1-A-24) to formula (B1-A-33), formula (B1-A-36) to formula (B1-A-40), formula (B1-A-47) to formula (B1-A-59) is more preferable. TIFF0007702806000053.tif87161

[0091] TIFF0007702806000054.tif124159

[0092] TIFF0007702806000055.tif101154

[0093] TIFF0007702806000056.tif64162

[0094] TIFF0007702806000057.tif111141

[0095] TIFF0007702806000058.tif86165

[0096] TIFF0007702806000059.tif100161 Here, R i2 ~R i7 is, independently of each other, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R i8 is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by combining these, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. L A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q 1 and Q 2 represent the same meaning as described above. Specific examples of the anion represented by formula (I-A) include the anions described in JP-A-2010-204646.

[0097] Preferred anions in the salt represented by formula (B1) include the anions represented by formula (B1a-1) to formula (B1a-38), respectively. TIFF0007702806000060.tif208160

[0098] TIFF0007702806000061.tif168155

[0099] Among them, an anion represented by any of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-16), formula (B1a-18), formula (B1a-19), formula (B1a-22) to formula (B1a-38) is preferred.

[0100] Z1 +Examples of the organic cation include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, and organic phosphonium cations. Among these, organic sulfonium cations and organic iodonium cations are preferred, and arylsulfonium cations are more preferred. Specifically, cations represented by any of formulas (b2-1) to (b2-4) (hereinafter, may be referred to as "cation (b2-1)" etc. according to the formula number) can be mentioned. TIFF0007702806000062.tif46170In formulas (b2-1) to (b2-4), R b4 ~R b6 each independently represents a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and the hydrogen atom contained in the chain hydrocarbon group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, or a glycidyloxy group, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. R b4 and R b5 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and -CH2- contained in the ring may be replaced with -O-, -S-, or -CO-. R b7 and R b8 each independently represents a halogen atom, a hydroxy group, 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 any of 0 to 5. When m2 is 2 or more, the plurality of R b7 may be the same or different, and when n2 is 2 or more, the plurality of Rb8 may be the same or different. R b9 and R b10 each independently represents a linear hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms. R b9 and R b10 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b11 represents a hydrogen atom, a linear hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 represents a linear hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the linear hydrocarbon group may be substituted by an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms. R b11 and R b12 may be bonded to each other to form a ring including the -CH-CO- to which they are bonded, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b13 ~R b18 each independently represents a halogen atom, a hydroxy group, a aliphatic hydrocarbon group having 1 to 12 carbon atoms, a fluorinated alkyl 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 any integer from 0 to 5. q2 and r2 each independently represent any integer from 0 to 4. u2 represents 0 or 1. When o2 is 2 or more, the plurality of R b13 are the same or different, and when p2 is 2 or more, the plurality of R b14are the same or different, and when q2 is 2 or more, a plurality of Rs b15 are the same or different, and when r2 is 2 or more, a plurality of Rs b16 are the same or different, and when s2 is 2 or more, a plurality of Rs b17 are the same or different, and when t2 is 2 or more, a plurality of Rs b18 are the same or different. The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples of the chain hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and 2-ethylhexyl group. In particular, R b9 ~R b12 The chain hydrocarbon group of is preferably C1-C12. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups. TIFF0007702806000063.tif10159 In particular, R b9 ~R b12 The alicyclic hydrocarbon group of is preferably C3-C18, more preferably C4-C12. Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include methylcyclohexyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, 2-ethyladamantan-2-yl group, 2-isopropyladamantan-2-yl group, methylnorbornyl group, and isobornyl group. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less. The alkyl fluoride group represents an alkyl group having 1 to 12 carbon atoms with a fluorine atom, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and a perfluorobutyl group. The number of carbon atoms in the alkyl fluoride group is preferably 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a biphenylyl group, a naphthyl group, and a phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples thereof include an aromatic hydrocarbon group having a chain hydrocarbon group with 1 to 18 carbon atoms (such as a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a p-ethylphenyl group, a p-tert-butylphenyl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group), and an aromatic hydrocarbon group having an alicyclic hydrocarbon group with 3 to 18 carbon atoms (such as a p-cyclohexylphenyl group and a p-adamantylphenyl group). In addition, when the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, a chain hydrocarbon group with 1 to 18 carbon atoms and an alicyclic hydrocarbon group with 3 to 18 carbon atoms are preferred. Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group. Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, and a 2-ethylhexylcarbonyloxy group. R b4 and R b5 The ring formed by R and R being bonded to each other together with the sulfur atom to which they are bonded may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated, and unsaturated rings. Examples of this ring include rings having 3 to 18 carbon atoms, preferably rings having 4 to 18 carbon atoms. Further, examples of the ring containing a sulfur atom include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings, and examples thereof include the following rings. * represents a bonding position. TIFF0007702806000064.tif23144R b9 and R b10 The ring formed by R and R together may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated, and unsaturated rings. Examples of this ring include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings. Examples thereof include a thiolan-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium ring. R b11 and R b12 The ring formed by R and R together may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated, and unsaturated rings. Examples of this ring include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings. Examples thereof include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

[0101] Among the cations (b2-1) to (b2-4), preferably, the cation (b2-1) is used. Examples of the cation (b2-1) include the following cations. TIFF0007702806000065.tif73149

[0102] TIFF0007702806000066.tif110165

[0103] Examples of the cation (b2-2) include the following cations and the like. TIFF0007702806000067.tif18150

[0104] Examples of the cation (b2-3) include the following cations and the like. TIFF0007702806000068.tif25122

[0105] Examples of the cation (b2-4) include the following cations and the like. TIFF0007702806000069.tif127165

[0106] The acid generator (B) is a combination of the above-mentioned anion and the above-mentioned organic cation, and these can be arbitrarily combined. Preferred examples of the acid generator (B) include a combination of an anion represented by any of the formulas (B1a-1) to (B1a-3), (B1a-7) to (B1a-16), (B1a-18), (B1a-19), (B1a-22) to (B1a-38) and the cation (b2-1), the cation (b2-3) or the cation (b2-4).

[0107] Preferred examples of the acid generator (B) include those represented by the formulas (B1-1) to (B1-56). Among them, those containing an arylsulfonium cation are preferred, and those represented by the formulas (B1-1) to (B1-3), (B1-5) to (B1-7), (B1-11) to (B1-14), (B1-20) to (B1-26), (B1-29), (B1-31) to (B1-56) are particularly preferred. TIFF0007702806000070.tif87150

[0108] TIFF0007702806000071.tif145158

[0109] TIFF0007702806000072.tif92153

[0110] TIFF0007702806000073.tif127143 TIFF0007702806000074.tif62163

[0111] TIFF0007702806000075.tif92158

[0112] In the resist composition of the present invention, the content of the carboxylate (I) is preferably 0.1% by mass or more and 35% by mass or less, more preferably 0.5% by mass or more and 30% by mass or less, and still more preferably 1% by mass or more and 25% by mass or less with respect to the solid content of the resist composition. In the resist composition of the present invention, the content of the acid generator (B) is preferably 1 part by mass or more and 45 parts by mass or less, more preferably 3 parts by mass or more and 40 parts by mass or less, and still more preferably 3 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the resin (A). The resist composition of the present invention may contain one kind of the acid generator (B) alone or a plurality of kinds thereof.

[0113] <Resin (A)> The resin (A) has a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)"). The resin (A) preferably further contains a structural unit other than the structural unit (a1). Examples of the structural unit other than the structural unit (a1) include a structural unit having no acid-labile group (hereinafter sometimes referred to as "structural unit (s)"), a structural unit other than the structural unit (a1) and the structural unit (s) (for example, a structural unit having a halogen atom described later (hereinafter sometimes referred to as "structural unit (a4)")), a structural unit having a non-leaving hydrocarbon group described later (hereinafter sometimes referred to as "structural unit (a5)"), and structural units derived from other monomers known in the art.

[0114] 〈Structural unit (a1)〉 The structural unit (a1) is derived from a monomer having an acid-labile group (hereinafter sometimes referred to as "monomer (a1)"). The acid-labile group contained in the resin (A) is preferably a group represented by the formula (1) (hereinafter also referred to as group (1)) and / or a group represented by the formula (2) (hereinafter also referred to as group (2)). TIFF0007702806000076.tif2397[In the formula (1), R a1 、R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, or R a1 and R a2 are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bonding position.] TIFF0007702806000077.tif2379[In the formula (2), R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2’ and R a3’ are bonded to each other to form a heterocyclic group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X, and -CH2- contained in the hydrocarbon group and the heterocyclic group may be replaced by -O- or -S-. X represents an oxygen atom or a sulfur atom. na’ represents 0 or 1. * represents a bond.]

[0115] R a1 、R a2 and R a3 Examples of the alkyl group in R a1 、Ra2 and R a3 Examples of the alkenyl group in include ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, octynyl group, isooctynyl group, nonenyl group. R a1 、R a2 and R a3 The alicyclic hydrocarbon group in, and may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group and the following group (* represents a bond). R a1 、R a2 and R a3 The number of carbon atoms of the alicyclic hydrocarbon group of, and is preferably 3 to 16. TIFF0007702806000078.tif10159R a1 、R a2 and R a3 Examples of the aromatic hydrocarbon group in, and include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group. Examples of the combined group include a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (e.g., alkylcycloalkyl group or cycloalkylalkyl group), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group. Preferably, ma is 0 and na is 1. R a1 and R a2 When and are bonded to each other to form an alicyclic hydrocarbon group, -C(R a1 )(R a2 )(Ra3 ) include the following groups. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * represents the bonding position with -O-. TIFF0007702806000079.tif31135

[0116] R a1’ , R a2’ and R a3’ Examples of the hydrocarbon group in R , R a1 , R a2 and R a3 include the same groups as those mentioned for R Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group, etc. Examples of the combined group include a group formed by combining the above-mentioned alkyl group and alicyclic hydrocarbon group (e.g., alkylcycloalkyl group or cycloalkylalkyl group), aralkyl group (such as benzyl group), aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), alicyclic hydrocarbon group having an aromatic hydrocarbon group (phenylcyclohexyl group, etc.), etc. R a2’ and R a3’ When R a1’ and R a2’ )-X-R a3’ combine with each other to form a heterocyclic group together with the carbon atom to which they are attached and X, examples of -C(R TIFF0007702806000080.tif21142R a1’ and R a2’ at least one of them is preferably a hydrogen atom. na' is preferably 0.

[0117] Examples of the group (1) include the following groups. In formula (1), R a1 , R a2 and R a3 are alkyl groups, ma = 0, and na = 1. As such a group, a tert-butoxycarbonyl group is preferable. In formula (1), R a1 , R a2 together with the carbon atom to which they are attached form an adamantyl group, and 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 is an adamantyl group, ma = 0, and na = 1. Specific examples of the group (1) include the following groups. * represents a bond. TIFF0007702806000081.tif170163

[0118] Specific examples of the group (2) include the following groups. * represents a bonding position. TIFF0007702806000082.tif74154

[0119] The monomer (a1) is preferably a monomer having an acid-labile group and an ethylenically unsaturated bond, more preferably a (meth)acrylic monomer having an acid-labile group.

[0120] Among the (meth)acrylic monomers having an acid-labile group, those having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are preferable. If a resin (A) having a structural unit derived from a monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in the resist composition, the resolution of the resist pattern can be improved.

[0121] As a structural unit derived from a (meth)acrylic monomer having a group (1), a structural unit represented by the formula (a1-0) (hereinafter, may be referred to as structural unit (a1-0)), a structural unit represented by the formula (a1-1) (hereinafter, may be referred to as structural unit (a1-1)), or a structural unit represented by the formula (a1-2) (hereinafter, may be referred to as structural unit (a1-2)) can be mentioned. Preferably, it is at least one or two structural units selected from the group consisting of structural unit (a1-1) and structural unit (a1-2). These may be used alone or in combination of two or more. TIFF0007702806000083.tif41139[In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 、L a1 and L a2 each independently represents -O- or * -O-(CH2) k1 -CO-O-, k1 represents an integer of 1 to 7, and * represents a bond to -CO-. R a01 、R a4 and R a5 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a02 、R a03 and R a04 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, 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.]

[0122] R a01, R a4 and R a5 is preferably a hydrogen atom or a methyl group, more preferably a methyl group. L a01 , L a1 and L a2 is preferably an oxygen atom or *-O-(CH2) k01 -CO-O- (wherein k01 is preferably any integer from 1 to 4, more preferably 1), and more preferably an oxygen atom. R a02 , R a03 and R a04 Examples of the alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and groups combining these in R a1 ~R a3 are the same groups as those exemplified by the groups in formula (1) R R a6 and R a7 Examples of the alkyl group, alkenyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and groups combining these in R a1 , R a2 and R a3 are the same groups as those exemplified by the groups in formula (1) R R a02 , R a03 , and R a04 The alkyl group in R R a6 and R a7 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. R a6 and R a7 The alkyl group in R R a02 , R a03 and R a04The number of carbon atoms of the alicyclic hydrocarbon group is preferably 5 to 12, more preferably 5 to 10. R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms of the aromatic hydrocarbon group of and R is preferably 6 to 12, more preferably 6 to 10. For the group combining an alkyl group and an alicyclic hydrocarbon group, it is preferable that the total number of carbon atoms of these combined alkyl group and alicyclic hydrocarbon group is 18 or less. For the group combining an alkyl group and an aromatic hydrocarbon group, it is preferable that the total number of carbon atoms of these combined alkyl group and aromatic hydrocarbon group is 18 or less. R a02 and R a03 are preferably an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a phenyl group or a naphthyl 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, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. R a6 and R a7 are preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group, a phenyl group or a naphthyl group, still more preferably an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group or a phenyl group. m1 is preferably any integer from 0 to 3, more preferably 0 or 1. n1 is preferably any integer from 0 to 3, more preferably 0 or 1. n1' is preferably 0 or 1.

[0123] Examples of the structural unit (a1-0) include structural units represented by any of formula (a1-0-1) to formula (a1-0-18) and R in the structural unit (a1-0)a01 Examples of the structural unit in which the methyl group corresponding to R is replaced with a hydrogen atom, a halogen atom, a haloalkyl group (alkyl group having a halogen atom), or another alkyl group include structural units represented by any of formula (a1-0-1) to formula (a1-0-10), formula (a1-0-13), and formula (a1-0-14), and the structural unit is preferably a structural unit represented by any of formula (a1-0-1) to formula (a1-0-10), formula (a1-0-13), and formula (a1-0-14). TIFF0007702806000084.tif99167

[0124] Examples of the structural unit (a1-1) include structural units derived from the monomers described in JP-A-2010-204646. Among them, the structural unit represented by any of formula (a1-1-1) to formula (a1-1-7) and R in the structural unit (a1-1) a4 The structural unit in which the methyl group corresponding to R is replaced with a hydrogen atom is preferable, and the structural unit represented by any of formula (a1-1-1) to formula (a1-1-4) is more preferable. TIFF0007702806000085.tif39167

[0125] Examples of the structural unit (a1-2) include structural units represented by any of formula (a1-2-1) to formula (a1-2-14) and structural units in which the methyl group corresponding to R in the structural unit (a1-2) a5 is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group, and the structural unit represented by any of formula (a1-2-2), formula (a1-2-5), formula (a1-2-6), and formula (a1-2-10) to formula (a1-2-14) is preferable. TIFF0007702806000086.tif66163

[0126] When the resin (A) contains the structural unit (a1-0), the content is usually 5 to 60 mol%, preferably 5 to 50 mol%, more preferably 10 to 40 mol% based on all the structural units of the resin (A). When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is usually 10 to 95 mol%, preferably 15 to 85 mol%, more preferably 15 to 80 mol%, still more preferably 20 to 80 mol%, and even more preferably 20 to 75 mol% based on all the structural units of the resin (A).

[0127] Examples of the structural unit having the group (2) in the structural unit (a1) include a structural unit represented by the formula (a1-4) (hereinafter, may be referred to as "structural unit (a1-4)"). TIFF0007702806000087.tif3854[In the formula (a1-4), R a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a33 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 alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 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 a30 represents a single bond or * -X a31 -(A a32 -X a32 ) nc - and * represents the bonding site with the carbon atom to which -R a32 is bonded. A a32 represents an alkanediyl group having 1 to 6 carbon atoms. X a31 and X a32 each independently represents -O-, -CO-O- or -O-CO-. nc represents 0 or 1. la represents any integer from 0 to 4. When la is any integer of 2 or more, a plurality of R a33 may be the same as or different from each other. R a34 and R a35each 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 bonded to each other to form, together with the -C-O- to which they are bonded, a divalent hydrocarbon group having 2 to 20 carbon atoms, and the -CH2- contained in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-.]

[0128] R a32 and R a33 Examples of the halogen atom in include fluorine atom, chlorine atom, bromine atom and the like. R a32 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in include trifluoromethyl group, difluoromethyl 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 and perfluorohexyl group. R a32 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a33 Examples of the alkyl group in include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group. R a33 Examples of the alkoxy group in include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably methoxy group or ethoxy group, and even more preferably methoxy group. Ra33 Examples of the alkoxyalkyl group in [reference] include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group. R a33 Examples of the alkoxyalkoxy group in [reference] include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethyl group or an ethoxyethyl group. R a33 Examples of the alkylcarbonyl group in [reference] include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group. R a33 Examples of the alkylcarbonyloxy group in [reference] include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group. R a33 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group, and even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0129] *-X a31 -(A a32 -X a32 ) nc- includes, *-O-, *-CO-O-, *-O-CO-, *-CO-O-A a32 -CO-O-, *-O-CO-A a32 -O-, *-O-A a32 -CO-O-, *-CO-O-A a32 -O-CO-, *-O-CO-A a32 -O-CO- are included. Among them, *-CO-O-, *-CO-O-A a32 -CO-O- or *-O-A a32 -CO-O- is preferred.

[0130] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. A a32 is preferably a methylene group or an ethylene group.

[0131] A a30 is preferably a single bond, *-CO-O- or *-CO-O-A a32 -CO-O-, more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferably a single bond or *-CO-O-.

[0132] la is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0. R a34 、R a35 and R a36 Examples of the hydrocarbon group in include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group combining these. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, etc. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* represents the bonding site). TIFF0007702806000088.tif10151Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group and the like. Examples of the combined group include a group formed by combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, cycloalkylalkyl group), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group and the like. In particular, R a36 Examples of R include an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these.

[0133] R a34 is preferably a hydrogen atom. R a35 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a methyl group or an ethyl group. R a36 The hydrocarbon group of R is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these, and more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. R a36The alkyl group and alicyclic hydrocarbon group in [the compound] are preferably unsubstituted. R a36 The aromatic hydrocarbon group in [the compound] preferably has an aromatic ring having an aryloxy group with 6 to 10 carbon atoms.

[0134] -OC(R a34 )(R a35 )-O-R a36 in the structural unit (a1-4) eliminates upon contact with an acid (e.g., p-toluenesulfonic acid) to form a hydroxy group. -OC(R a34 )(R a35 )-O-R a36 is preferably bonded to the o-position or p-position of the benzene ring, and more preferably bonded to the p-position.

[0135] Examples of the structural unit (a1-4) include structural units derived from the monomers described in JP-A-2010-204646. Preferably, there are structural units represented by formula (a1-4-1) to formula (a1-4-18) and structural units in which the hydrogen atom corresponding to R a32 in the structural unit (a1-4) is replaced by a halogen atom, a haloalkyl group or an alkyl group, and more preferably, there are structural units represented by formula (a1-4-1) to formula (a1-4-5), formula (a1-4-10), formula (a1-4-13), and formula (a1-4-14). When the resin (A) has the structural unit (a1-4), its content is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, and even more preferably 10 to 40 mol% based on the total of all the structural units of the resin (A).

[0136] Examples of the structural unit derived from the (meth)acrylic monomer having the group (2) also include a structural unit represented by formula (a1-5) (hereinafter sometimes referred to as "structural unit (a1-5)"). TIFF0007702806000090.tif4354In formula (a1-5), R a8represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. Z a1 is a single bond or *-(CH2) h3 -CO-L 54 -, h3 represents an integer of any one of 1 to 4, and * represents the bonding position with 51 L. L 51 L 52 L 53 and L 54 each independently represents -O- or -S-. s1 represents an integer of any one of 1 to 3. s1’ represents an integer of any one of 0 to 3.

[0137] Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is 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, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluoromethyl group and a trifluoromethyl group. In formula (a1-5), R a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group. L 51 is preferably an oxygen atom. L 52 and L 53 Among them, it is preferable that one is -O- and the other is -S-. s1 is preferably 1. s1’ is preferably an integer of any one of 0 to 2. Z a1 is preferably a single bond or *-CH2-CO-O-.

[0138] Examples of the structural unit (a1-5) include structural units derived from monomers described in JP-A-2010-61117. Among them, the structural units represented by formula (a1-5-1) to formula (a1-5-4) are preferable, and the structural unit represented by formula (a1-5-1) or formula (a1-5-2) is more preferable. When the resin (A) has the structural unit (a1-5), its content is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, still more preferably 5 to 40 mol%, and even more preferably 5 to 30 mol% based on all the structural units of the resin (A).

[0139] Examples of the structural unit (a1) also include the following structural units. When the resin (A) contains the above structural unit, its content is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, and still more preferably 10 to 40 mol% based on all the structural units of the resin (A).

[0140] 〈Structural unit (s)〉 The structural unit (s) is derived from a monomer having no acid-labile group (hereinafter sometimes referred to as "monomer (s)"). As the monomer that leads to the structural unit (s), a monomer having no acid-labile group known in the resist field can be used. The structural unit (s) preferably has a hydroxy group or a lactone ring. By using a resin having a structural unit having a hydroxy group and no acid-labile group (hereinafter sometimes referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and no acid-labile group (hereinafter sometimes referred to as "structural unit (a3)") in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

[0141] 〈Structural unit (a2)〉 The hydroxy group of the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. When producing a resist pattern from the resist composition of the present invention, when using a high-energy ray such as a KrF excimer laser (248 nm), an electron beam, or EUV (extreme ultraviolet light) as an exposure light source, as the structural unit (a2), a structural unit (a2) having a phenolic hydroxy group is preferable, and it is more preferable to use the structural unit (a2-A) described later. When using an ArF excimer laser (193 nm) or the like, as the structural unit (a2), a structural unit (a2) having an alcoholic hydroxy group is preferable, and it is more preferable to use the structural unit (a2-1) described later. The structural unit (a2) may be included alone as one kind, or may include two or more kinds.

[0142] Examples of the structural unit having a phenolic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a2-A) (hereinafter sometimes referred to as "structural unit (a2-A)"). TIFF0007702806000093.tif4146[In the 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 alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 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 represents a single bond or *-X a51 -(A a52 -X a52 ) nb -, where * represents the bonding position with the carbon atom to which -R a50 is bonded. 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 any integer from 0 to 4. When mb is any integer of 2 or more, a plurality of Rs a51 may be the same as or different from each other.]

[0143] R a50 and R a51 Examples of the halogen atom in R include a fluorine atom, a chlorine atom, and a bromine atom. R a50 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, and a perfluorohexyl group. R a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a51 Examples of the alkyl group in R include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R a51 Examples of the alkoxy group in R include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group. R a51Examples of the alkoxyalkyl group include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group. R a51 Examples of the alkoxyalkoxy group include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a methoxyethoxy group or an ethoxyethoxy group. R a51 Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, more preferably an acetyl group. R a51 Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, more preferably an acetyloxy group. R a51 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group, and even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0144] *-X a51 -(A a52 -X a52 ) nb- includes, *-O-, *-CO-O-, *-O-CO-, *-CO-O-A a52 -CO-O-, *-O-CO-A a52 -O-, *-O-A a52 -CO-O-, *-CO-O-A a52 -O-CO-, *-O-CO-A a52 -O-CO- are included. Among them, *-CO-O-, *-CO-O-A a52 -CO-O- or *-O-A a52 -CO-O- is preferred. Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. A a52 is preferably a methylene group or an ethylene group. A a50 is a single bond, *-CO-O- or *-CO-O-A a52 -CO-O- is preferred, more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferably a single bond or *-CO-O-. mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0. The hydroxy group is preferably bonded to the ortho position or the para position of the benzene ring, and more preferably bonded to the para position.

[0145] Examples of the structural unit (a2-A) include structural units derived from monomers described in JP-A-2010-204634 and JP-A-2012-12577. Examples of the structural unit (a2-A) include the structural units represented by formula (a2-2-1) to formula (a2-2-16), and R in the structural unit (a2-A) in the structural units represented by formula (a2-2-1) to formula (a2-2-16). a50Examples of the structural unit in which the methyl group corresponding to [[ID=]] is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group. The structural unit (a2-A) is the structural unit represented by the formula (a2-2-1), the structural unit represented by the formula (a2-2-3), the structural unit represented by the formula (a2-2-6), the structural unit represented by the formula (a2-2-8), the structural units represented by the formulas (a2-2-12) to (a2-2-14), and in the structural units represented by the formula (a2-2-1), the structural unit represented by the formula (a2-2-3), the structural unit represented by the formula (a2-2-6), the structural unit represented by the formula (a2-2-8), the structural units represented by the formulas (a2-2-12) to (a2-2-14), R in the structural unit (a2-A) a50 is preferably a structural unit in which the methyl group corresponding to [[ID=]] is replaced with a hydrogen atom, and in the structural unit represented by the formula (a2-2-3), the structural unit represented by the formula (a2-2-8), the structural units represented by the formulas (a2-2-12) to (a2-2-14), and the structural unit represented by the formula (a2-2-3) or the structural unit represented by the formula (a2-2-8), the structural units represented by the formulas (a2-2-12) to (a2-2-14), R in the structural unit (a2-A) a50 is more preferably a structural unit in which the methyl group corresponding to [[ID=]] is replaced with a hydrogen atom, and in the structural unit represented by the formula (a2-2-8) and the structural unit represented by the formula (a2-2-8), R in the structural unit (a2-A) a50 is even more preferably a structural unit in which the methyl group corresponding to [[ID=]] is replaced with a hydrogen atom. When the structural unit (a2-A) is contained in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, even more preferably 15 to 65 mol%, and even more preferably 20 to 65 mol% with respect to all the structural units. The structural unit (a2-A) can be incorporated into the resin (A) by, for example, polymerizing using the structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. Also, after polymerizing using acetoxystyrene or the like and then treating with an alkali such as tetramethylammonium hydroxide, the structural unit (a2-A) can be incorporated into the resin (A).

[0146] Examples of the structural unit having an alcoholic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)"). In the formula (a2-1) in TIFF0007702806000095.tif3957, L a3 represents -O- or * -O-(CH2) k2 -CO-O-, k2 represents an integer of any one of 1 to 7. * represents the bonding position with -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 each independently represent a hydrogen atom, a methyl group or a hydroxy group. o1 represents an integer of any one of 0 to 10.

[0147] In the formula (a2-1), L a3 is preferably -O-, -O-(CH2) f1 -CO-O- (wherein f1 represents an integer of any one of 1 to 4), 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 any one of 0 to 3, more preferably 0 or 1.

[0148] Examples of the structural unit (a2-1) include structural units derived from monomers described in JP 2010-204646 A. A structural unit represented by any one of formulas (a2-1-1) to (a2-1-6) is preferred, a structural unit represented by any one of formulas (a2-1-1) to (a2-1-4) is more preferred, and a structural unit represented by formula (a2-1-1) or formula (a2-1-3) is even more preferred. TIFF0007702806000096.tif54149 When resin (A) contains the structural unit (a2-1), the content thereof is usually 1 to 45 mol %, preferably 1 to 40 mol %, more preferably 1 to 35 mol %, even more preferably 2 to 20 mol %, and still more preferably 2 to 10 mol %, based on all structural units of resin (A).

[0149] <Structural unit (a3)> The lactone ring of the structural unit (a3) ​​may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring, or a δ-valerolactone ring, or may be a condensed ring of a monocyclic lactone ring and another ring. Preferred examples include a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)). The structural unit (a3) ​​is preferably a structural unit represented by formula (a3-1), (a3-2), (a3-3) or (a3-4). One of these may be contained alone, or two or more of them may be contained. TIFF0007702806000097.tif50157 [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-OLa9 -CO-O- or *-O-L a8 -O-CO-L a9 -O- represents. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * represents 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 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or 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 an aliphatic hydrocarbon group having 1 to 4 carbon atoms. p1 represents any integer from 0 to 5. q1 represents any integer from 0 to 3. r1 represents any integer from 0 to 3. w1 represents any integer from 0 to 8. When p1, q1, r1 and / or w1 is 2 or more, a plurality of R a21 、R a22 、R a23 and / or R a25 may be the same as or different from each other.

[0150] R a21 、R a22 、R a23 and R a25 Examples of the aliphatic hydrocarbon group in R a24Examples of the halogen atom in [context] include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R a24 Examples of the alkyl group in [context] include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group, etc. Preferably, an alkyl group having 1 to 4 carbon atoms is exemplified, and more preferably, a methyl group or an ethyl group is exemplified. R a24 Examples of the alkyl group having a halogen atom in [context] include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, etc.

[0151] L a8 and L a9 Examples of the alkanediyl group in [context] and [context] include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group, etc.

[0152] In Formula (a3-1) to Formula (a3-3), L a4 ~L a6 are each independently, preferably -O- or, *-O-(CH2) k3 -CO-O- wherein k3 is an integer of 1 to 4, more preferably -O- and, *-O-CH2-CO-O-, and even more preferably an oxygen atom. 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. p1, q1, and r1 are each independently preferably an integer of any one of 0 to 2, more preferably 0 or 1.

[0153] In formula (a3-4), R a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, and still more preferably 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 *-O-L a8 -CO-O-, more preferably -O-, -O-CH2-CO-O-, or -O-C2H4-CO-O-. w1 is preferably an integer of any one of 0 to 2, more preferably 0 or 1. In particular, formula (a3-4) is preferably formula (a3-4)’. TIFF0007702806000098.tif4051 (wherein R a24 , L a7 represents the same meaning as described above.)

[0154] Examples of the structural unit (a3) include structural units derived from the monomers described in JP-A-2010-204646, the monomers described in JP-A-2000-122294, and the monomers described in JP-A-2012-41274. Examples of the structural unit (a3) include structural units represented by any of 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 (a3-4-12), and, in the above structural units, structural units in which the methyl groups corresponding to R a18 , R a19 , R a20 and R a24 are replaced with hydrogen atoms are preferred. TIFF0007702806000099.tif117165

[0155] When the resin (A) contains the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, more preferably 10 to 60 mol% based on all the structural units of the resin (A). Also, the content of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit (a3-4) is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, still more preferably 10 to 50 mol% based on all the structural units of the resin (A), respectively.

[0156] 〈Structural unit (a4)〉 Examples of the structural unit (a4) include the following structural units. TIFF0007702806000100.tif3165[In the formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having a fluorine atom and having 1 to 24 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-.] R 42 Examples of the saturated hydrocarbon group represented by include a chain hydrocarbon group, a monocyclic or polycyclic alicyclic hydrocarbon group, and a group formed by combining these.

[0157] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group. Examples of the monocyclic or polycyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents the bonding position). As the group formed by 11160 combinations, groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups can be mentioned, such as -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group-alkyl group, etc.

[0158] As the structural unit (a4), structural units represented by at least one selected from the group consisting of formula (a4-0), formula (a4-1), formula (a4-2), formula (a4-3) and formula (a4-4) can be mentioned. TIFF0007702806000102.tif3953[In formula (a4-0), R 5a 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 represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms. R 6a represents a hydrogen atom or a fluorine atom.]

[0159] L 4a As the alkanediyl group in, linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, and branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group can be mentioned.

[0160] L 3aExamples of the perfluoroalkanediyl group in [description] include difluoromethylene group, perfluoroethylene group, perfluoropropane-1,1-diyl 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 Examples of the perfluorocycloalkanediyl group in [description] include perfluorocyclohexanediyl group, perfluorocyclopentanediyl group, perfluorocycloheptanediyl group, perfluoroadamantanediyl group, and the like.

[0161] L 4a is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond or a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0162] Examples of the structural unit (a4-0) include the structural units shown below and the structural units in the following structural units where the methyl group corresponding to R in the structural unit (a4-0) is replaced by a hydrogen atom. 5a are exemplified. TIFF0007702806000103.tif97166

[0163] TIFF0007702806000104.tif5170In 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, and -CH2- contained in the saturated 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 formula (a-g1). However, at least one of A a41 and R a42 has a halogen atom (preferably a fluorine atom) as a substituent. TIFF0007702806000105.tif1383[In formula (a-g1), s represents 0 or 1. A a42 and A a44 each independently represent a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. A a43 represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. X a41 and X a42 each independently represent -O-, -CO-, -CO-O- or -O-CO-. However, the total number of carbon atoms of A a42 , A a43 , A a44 , X a41 and X a42 is 7 or less. ] * represents a bonding position, and the * on the right side is the bonding position with -O-CO-R a42 . ]

[0164] Examples of the saturated hydrocarbon group in R a42 include a chain saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and a group formed by combining these.

[0165] Examples of the chain saturated hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group. Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; polycyclic alicyclic saturated hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group, and the following group (* represents the bonding position). Examples of the group formed by the combination of TIFF0007702806000106.tif11160 include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic saturated hydrocarbon groups, such as -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group, etc.

[0166] R a42 Examples of the substituent that R has include at least one selected from the group consisting of a halogen atom and a group represented by the formula (a-g3). Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom, and preferably a fluorine atom. TIFF0007702806000107.tif752[In the formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-. A a45 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. * is the bonding site with R a42 However, in R a42 -X a43 -A a45 , when R a42 does not have a halogen atom, A a45 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which has at least one halogen atom. ​

[0167] A a45 Examples of the aliphatic hydrocarbon group in [context not clear] include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group; monocyclic alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group, and the following group (* represents the bonding position). TIFF0007702806000108.tif11160

[0168] R a42 R is preferably a saturated hydrocarbon group which may have a halogen atom, more preferably an alkyl group having a halogen atom and / or a saturated hydrocarbon group having a group represented by the formula (a-g3). R a42 When R is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, still more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the perfluoroalkyl group include perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, and perfluorooctyl group. Examples of the perfluorocycloalkyl group include perfluorocyclohexyl group. R a42 When R is a saturated hydrocarbon group having a group represented by the formula (a-g3), including the carbon atoms contained in the group represented by the formula (a-g3), the total carbon number of R a42 is preferably 15 or less, more preferably 12 or less. When having a group represented by the formula (a-g3) as a substituent, the number thereof is preferably 1.

[0169] R a42 When R is a saturated hydrocarbon group having a group represented by the formula (a-g3), a42 it is more preferably a group represented by the formula (a-g2). TIFF0007702806000109.tif874[In the formula (a-g2), A a46 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. X a44 represents **-O-CO- or **-CO-O- (** represents the bonding site with A a46 ).). A a47 represents an aliphatic 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 of is 18 or less, and among A a46 and A a47 at least one of them has at least one halogen atom. * represents the bonding position with the carbonyl group.]

[0170] A a46 the number of carbon atoms of the saturated hydrocarbon group of is preferably 1 to 6, more preferably 1 to 3. A a47 the number of carbon atoms of the aliphatic hydrocarbon group of is preferably 4 to 15, more preferably 5 to 12, and A a47 is more preferably a cyclohexyl group or an adamantyl group.

[0171] The preferred structure of the group represented by the formula (a-g2) is the following structure (* is the bonding position with the carbonyl group). TIFF0007702806000110.tif13161

[0172] A a41Examples of the alkanediyl group include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group; and branched alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group. A a41 Examples of the substituent in the alkanediyl group represented by A include hydroxy group and alkoxy groups having 1 to 6 carbon atoms. A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and even more preferably an ethylene group.

[0173] A in the group represented by formula (a-g1) a42 、A a43 and A a44 Examples of the divalent saturated hydrocarbon group represented by include linear or branched alkanediyl groups, monocyclic or polycyclic divalent alicyclic hydrocarbon groups, and groups formed by combining an alkanediyl group and a divalent alicyclic hydrocarbon group. Specifically, examples include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, etc. A a42 、A a43 and A a44 Examples of the substituent of the divalent saturated hydrocarbon group represented by include hydroxy group and alkoxy groups having 1 to 6 carbon atoms. s is preferably 0.

[0174] In the group represented by formula (a-g1), examples of the group in which X a42 is -O-, -CO-, -CO-O- or -O-CO- include the following groups. In the following examples, * and ** each represent a bonding position, and ** is -O-CO-Ra42 is the bonding site with TIFF0007702806000111.tif48153

[0175] Examples of the structural unit represented by formula (a4-1) include the following structural units and the structural units represented by formula (a4-1) in the following structural units, where the methyl group corresponding to R a41 is replaced by a hydrogen atom.

[0176] TIFF0007702806000112.tif100142

[0177] TIFF0007702806000113.tif123141

[0178] As the structural unit represented by formula (a4-1), the structural unit represented by formula (a4-2) is preferred. TIFF0007702806000114.tif3048[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, and -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-. R f6 represents a saturated hydrocarbon group having a fluorine atom and 1 to 20 carbon atoms. However, the upper limit of the total carbon number of L 44 and R f6 is 21.]

[0179] L 44 The alkanediyl group of is the same as the group exemplified by A a41 R f6 The saturated hydrocarbon group of is the same as the group exemplified by R a42 L 44 As the alkanediyl group in, an alkanediyl group having 2 to 4 carbon atoms is preferred, and an ethylene group is more preferred. ​​

[0180] Examples of the structural unit represented by formula (a4-2) include structural units represented by formulas (a4-1-1) to (a4-1-11), respectively. In the structural unit (a4-2), the methyl group corresponding to R f5 replaced by a hydrogen atom is also included as a structural unit represented by formula (a4-2).

[0181] TIFF0007702806000115.tif5164[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. X f12 represents *-O-CO- or *-CO-O- (* represents the bonding position with A f13 ).) A f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom. However, at least one of A f13 and A f14 has a fluorine atom, and the upper limit of the total number of carbon atoms of L 5 , A f13 and A f14 is 20.]

[0182] Examples of the alkanediyl group in L 5 include the same groups as those exemplified for the alkanediyl group of A a41 . A f13 The divalent saturated hydrocarbon group which may have a fluorine atom in preferably includes a divalent chain saturated hydrocarbon group which may have a fluorine atom and a divalent alicyclic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group. Examples of the divalent chain hydrocarbon group which may have a fluorine atom include alkane diyl groups such as methylene group, ethylene group, propane diyl group, butane diyl group and pentane diyl group; perfluoro alkane diyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropane diyl group, perfluorobutane diyl group and perfluoropentane diyl group, etc. The divalent alicyclic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic group include cyclohexane diyl group and perfluorocyclohexane diyl group, etc. Examples of the polycyclic group include adamantane diyl group, norbornane diyl group, perfluoroadamantane diyl group, etc.

[0183] A f14 Examples of the saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom of a42 are the same groups as those exemplified by R. Among them, alkyl fluoride groups such as trifluoromethyl group, difluoromethyl 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 perfluorooctyl group; cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantylmethyl group, etc. are preferable.

[0184] In formula (a4-3), L 5 is preferably an ethylene group. A f13The divalent saturated hydrocarbon group preferably includes a divalent chain hydrocarbon group having 1 to 6 carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a divalent chain hydrocarbon group having 2 to 3 carbon atoms. A f14 The saturated hydrocarbon group preferably includes a chain hydrocarbon group having 3 to 12 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a group including a chain hydrocarbon group having 3 to 10 carbon atoms and an alicyclic hydrocarbon group having 3 to 10 carbon atoms. Among them, A f14 is preferably a group including an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

[0185] Examples of the structural unit represented by the formula (a4-3) include structural units represented by the formulas (a4-1'-1) to (a4-1'-11), respectively. The methyl group corresponding to R f7 in the structural unit (a4-3) replaced by a hydrogen atom is also included as a structural unit represented by the formula (a4-3).

[0186] Examples of the structural unit (a4) also include a structural unit represented by the formula (a4-4). TIFF0007702806000116.tif3960 [In the formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 represents -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 - or -(CH2) j4 -CO-O-(CH2) j5 -. 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 having a fluorine atom.

[0187] R f22 The saturated hydrocarbon group of a42Examples of the saturated hydrocarbon group represented by are the same as those of R. f22 R is preferably an alkyl group having 1 to 10 carbon atoms or an alicyclic hydrocarbon group having 1 to 10 carbon atoms, each having a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom, and even more preferably an alkyl group having 1 to 6 carbon atoms having a fluorine atom. In formula (a4-4), A f21 is preferably -(CH2) j1 -, more preferably an ethylene group or a methylene group, and even more preferably a methylene group.

[0188] Examples of the structural unit represented by formula (a4-4) include the following structural units and the structural units represented by the following formulas, in which the methyl group corresponding to R in structural unit (a4-4) is replaced by a hydrogen atom. f21 are mentioned. When the resin (A) has the structural unit (a4), its content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol% based on all the structural units of the resin (A).

[0189] 〈Structural unit (a5)〉 Examples of the non-leaving hydrocarbon group of the structural unit (a5) include groups having a linear, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) preferably has a group having an alicyclic hydrocarbon group. Examples of the structural unit (a5) include the structural unit represented by formula (a5-1). TIFF0007702806000118.tif3972 [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 hydrogen atoms contained in the alicyclic hydrocarbon group may be substituted with aliphatic hydrocarbon groups having 1 to 8 carbon atoms. L 55represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-.

[0190] R 52 The alicyclic hydrocarbon group in 52 may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, and a 2-ethylhexyl group. Examples of the alicyclic hydrocarbon group having a substituent include a 3-methyladamantyl group. R 52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, more preferably an adamantyl group, a norbornyl group, or a cyclohexyl group.

[0191] L 55 Examples of the divalent saturated hydrocarbon group in 55 include a divalent chain saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and preferably a divalent chain saturated hydrocarbon group. Examples of the divalent chain saturated hydrocarbon group include alkanediyl groups such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group, and a pentanediyl group. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include cycloalkanediyl groups such as a cyclopentanediyl group and a cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantanediyl group and a norbornanediyl group.

[0192] L 55Examples of the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced by -O- or -CO- include groups represented by formula (L1-1) to formula (L1-4). In the following formulas, * and ** represent bonding positions, and * represents the bonding position with an oxygen atom. In formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents the bonding position with L x1 .). 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, the total number of carbon atoms of L x1 and L x2 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, the total number of carbon atoms of L x3 and L x4 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 represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms. However, the total number of carbon atoms of L x5 , L x6 and L x7 is 15 or less. In formula (L1-4), L x8 and L x9 each represent 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 x9 and W x1 have a total carbon number of 15 or less.

[0193] L x1 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably 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 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 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. 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 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 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.

[0194] Examples of the group represented by the formula (L1-1) include, for example, the following divalent groups. TIFF0007702806000120.tif54134

[0195] Examples of the group represented by formula (L1-2) include the following divalent groups. TIFF0007702806000121.tif24131

[0196] Examples of the group represented by formula (L1-3) include the following divalent groups. TIFF0007702806000122.tif15145

[0197] Examples of the group represented by formula (L1-4) include the following divalent groups. TIFF0007702806000123.tif26114L 55 is preferably a single bond or a group represented by formula (L1-1).

[0198] Examples of the structural unit (a5-1) include the following structural units and the structural units (a5-1) in the following structural units where the methyl group corresponding to R 51 is replaced by a hydrogen atom. TIFF0007702806000124.tif110150 When the resin (A) has the structural unit (a5), its content is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 3 to 15 mol% based on all the structural units of the resin (A).

[0199] 〈Structural unit (a6)〉 The structural unit (a6) is a structural unit having a -SO2- group, and preferably has a -SO2- group in the side chain. The structural unit having a -SO2- group may have a linear structure having a -SO2- group, a branched structure having a -SO2- group, or a cyclic structure (monocyclic and polycyclic structures) having a -SO2- group. Preferably, it is a structural unit having a cyclic structure having a -SO2- group, and more preferably, it is a structural unit having a cyclic structure containing -SO2-O- (sultone ring).

[0200] As the sultone ring, the following formula (T 1 -1), formula (T 1 -2), formula (T 1 -3) and formula (T 1 -4) are exemplified. The bonding site can be at any position. The sultone ring may be monocyclic, but is preferably polycyclic. The polycyclic sultone ring means a bridged ring containing -SO2-O- as an atomic group constituting the ring, and examples include the rings represented by formula (T 1 -1) and formula (T 1 -2). The sultone ring may further contain a heteroatom in addition to -SO2-O- as an atomic group constituting the ring, like the ring represented by formula (T 1 -2). Examples of the heteroatom include an oxygen atom, a sulfur atom or a nitrogen atom, and preferably an oxygen atom. TIFF0007702806000125.tif3187

[0201] The sultone ring may have a substituent, and examples of the substituent include an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, and an alkylcarbonyl group having 2 to 4 carbon atoms.

[0202] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group and a decyl group, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group. Examples of the alkyl group having a halogen atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group. Preferably, a trifluoromethyl group is mentioned. Examples of the alkyl group having a hydroxy group include a hydroxymethyl group and a hydroxyalkyl group such as a 2-hydroxyethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a tolyl group, a xylyl group, a cumyl group, a mesityl group, a biphenyl group, a phenanthryl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group. Examples of the alkoxycarbonyl group include a group in which an alkoxy group such as a methoxycarbonyl group and an ethoxycarbonyl group is bonded to a carbonyl group. Preferably, an alkoxycarbonyl group having 6 or less carbon atoms is mentioned, and more preferably, a methoxycarbonyl group is mentioned. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.

[0203] From the viewpoint that the production of the monomer leading to the structural unit (a6) is easy, a sultone ring having no substituent is preferable. As the sultone ring, a ring represented by the following formula (T1') is preferable. TIFF0007702806000126.tif3172[In the formula (T1'), X 11represents an oxygen atom, a sulfur atom or a methylene group. R 41 represents an alkyl group having 1 to 12 carbon atoms, which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms. ma represents any integer from 0 to 9. When ma is 2 or more, a plurality of R 41 may be the same or different. The bonding site is at an arbitrary position. X 11 is preferably an oxygen atom or a methylene group, more preferably a methylene group. R 41 Examples of R

[0204] As the sultone ring, a ring represented by the formula (T1) is more preferable. TIFF0007702806000127.tif3149[In the formula (T1), R 8 represents an alkyl group having 1 to 12 carbon atoms, which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms. m represents any integer from 0 to 9. When m is 2 or more, a plurality of R 8 may be the same or different. The bonding site is at an arbitrary position.

[0205] R 8 is the same as R 41 and the like can be mentioned. In formula (T1’), ma and in formula (T1), m are preferably 0 or 1, more preferably 0.

[0206] Examples of the ring represented by formula (T1’) and the ring represented by formula (T1) include the following rings. The bonding site can be at any position. TIFF0007702806000128.tif57165

[0207] The structural unit having a sultone ring preferably has the following group. * in the following group represents the bonding site. TIFF0007702806000129.tif51165

[0208] The structural unit having a -SO2- group preferably further has a group derived from a polymerizable group. Examples of the polymerizable group include a vinyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, an acryloylthio group, a methacryloylthio group, and the like. Among them, the monomer that leads to the structural unit (a6) is preferably a monomer having an ethylenically unsaturated bond, more preferably a (meth)acrylic monomer.

[0209] The structural unit (a6) is preferably a structural unit represented by formula (Ix). TIFF0007702806000130.tif4956[In formula (Ix), R x represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. A xx represents an oxygen atom, -N(R c )- or a sulfur atom. A x represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -N(R d )-. X 11 represents an oxygen atom, a sulfur atom or a methylene group. R 41 represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms. ma represents any integer from 0 to 9. When ma is 2 or more, a plurality of R 41 may be the same or different. R c and R d each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0210] R x Examples of the halogen atom of R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R x Examples of the alkyl group of R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and an n-hexyl group, etc. Preferably it is an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. R x Examples of the alkyl group having a halogen atom of R include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group and a triiodomethyl group, etc. R x is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group.

[0211] A xExamples of the divalent saturated hydrocarbon group include linear alkanediyl groups, branched alkanediyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and combinations of two or more of these groups may also be used. Specific examples include linear alkanediyl groups such as 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, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, and propane-2,2-diyl group; branched alkanediyl groups such as butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group; monocyclic divalent alicyclic saturated hydrocarbon groups which are cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, and cyclooctane-1,5-diyl group; polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group, etc.

[0212] R 41 、X 11 And ma are the same as those in formula (T1’). Examples of the sultone ring include those described above, and among them, those with specific bonding positions are preferred.

[0213] Examples of the structural unit (a6) include the following structural units. TIFF0007702806000131.tif104168

[0214] Among them, the structural units represented by formula (a6-1), formula (a6-2), formula (a6-6), formula (a6-7), formula (a6-8) and formula (a6-12) are preferable, and the structural units represented by formula (a6-1), formula (a6-2), formula (a6-7) and (a6-8) are more preferable. When the resin (A) has the structural unit (a6), its content is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, and still more preferably 3 to 30 mol% based on all the structural units of the resin (A).

[0215] <Structural unit (II)> The resin (A) may further contain a structural unit that decomposes upon exposure to generate an acid (hereinafter sometimes referred to as "structural unit (II)"). Specific examples of the structural unit (II) include the structural units described in JP-A-2016-79235, and it is preferably a structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain or a structural unit having a sulfonio group and an organic anion in the side chain.

[0216] The structural unit having a sulfonate group or a carboxylate group in the side chain is preferably a structural unit represented by formula (II-2-A'). TIFF0007702806000132.tif36104[In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-, and a hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom or a hydroxy group. A x1 represents an alkanediyl group having 1 to 8 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted by a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. RA -represents a sulfonate group or a carboxylate group. R III3 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. ZA + represents an organic cation.

[0217] R III3 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R III3 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R include the same ones as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R. a8 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R include the same ones as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R. A x1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by A include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, and the like. A x1 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted on A include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, a perfluorohexyl group, and the like. X III3 Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and combinations thereof. Specifically, linear alkanediyl groups such as 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; branched alkanediyl groups such as butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; divalent polycyclic alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. can be mentioned. Examples of those in which -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- include divalent groups represented by formula (X1) to formula (X53). However, the number of carbon atoms before -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- is 17 or less, respectively. In the following formula, * and ** represent bonding sites, and * represents a bond to A x1 and represents a bond to A. TIFF0007702806000133.tif145161

[0218] 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. X 6 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 8represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

[0219] ZA in formula (II-2-A’) + is the same as the cation Z1 in the acid generator (B1). + Examples thereof include the same ones.

[0220] The structural unit represented by formula (II-2-A’) is preferably the structural unit represented by formula (II-2-A). TIFF0007702806000134.tif38109 [In formula (II-2-A), R III3 , X III3 and ZA + represent the same meaning as described above. z2A represents any integer from 0 to 6. R III2 and R III4 each independently represent a hydrogen atom, a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. When z2A is 2 or more, a plurality of R III2 and R III4 may be the same as or different from each other. Q a and Q b each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.] R III2 , R III4 , Q a and Q b Examples of the perfluoroalkyl group having 1 to 6 carbon atoms represented by b1 are the same as those of the perfluoroalkyl group having 1 to 6 carbon atoms represented by the aforementioned Q

[0221] The structural unit represented by formula (II-2-A) is preferably the structural unit represented by formula (II-2-A-1). TIFF0007702806000135.tif5578 [In formula (II-2-A-1), R III2 , R III3 , R III4 , Q a , Qb and ZA + represents the same meaning as described above. R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. z2A1 represents any integer from 0 to 6. X I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, wherein -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-, and a hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom or a hydroxy group. R III5 Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by R include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group. X I2 Examples of the divalent saturated hydrocarbon group represented by X include the same as those of the divalent saturated hydrocarbon group represented by X III3 represented by.

[0222] As the structural unit represented by the formula (II-2-A-1), the structural unit represented by the formula (II-2-A-2) is more preferable. TIFF0007702806000136.tif5288 [In the formula (II-2-A-2), R III3 R III5 and ZA + represent the same meaning as described above. mA and nA each independently represent 1 or 2.

[0223] Examples of the structural unit represented by the formula (II-2-A') include, for example, the following structural units, R III3 wherein a group corresponding to the methyl group of is replaced by a hydrogen atom, a halogen atom (for example, a fluorine atom) or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom (for example, a trifluoromethyl group, etc.), and the structural units described in WO 2012 / 050015. ZA+ represents an organic cation. TIFF0007702806000137.tif86164

[0224] The structural unit having a sulfonio group and an organic anion in the side chain is preferably a structural unit represented by the formula (II-1-1). TIFF0007702806000138.tif3791[In the 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 represent a hydrocarbon group having 1 to 18 carbon atoms, and R II2 and R II3 may combine with each other to form a ring together with the sulfur atom to which they are attached. R II4 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. A - represents an organic anion.] R II1 Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R include a phenylene group and a naphthylene group. R II2 and R II3 Examples of the hydrocarbon group represented by include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these. R II4 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R II4 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R are the same as those of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R a8 A II1 ​Examples of the divalent linking group represented by include divalent saturated hydrocarbon groups having 1 to 18 carbon atoms, and the -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O-, -S- or -CO-. Specifically, X III3 include the same ones as the divalent saturated hydrocarbon groups having 1 to 18 carbon atoms represented by .

[0225] Examples of the structural unit containing the cation in formula (II-1-1) include the structural unit represented by the following and the group corresponding to the methyl group of R II4 structural units in which the group corresponding to the methyl group of is replaced by a hydrogen atom, a fluorine atom, a trifluoromethyl group, etc. TIFF0007702806000139.tif107166

[0226] A - Examples of the organic anion represented by include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, carboxylic acid anions, etc. A - The organic anion represented by is preferably a sulfonate anion, and more preferably an anion contained in the salt represented by the aforementioned formula (B1).

[0227] A - Examples of the sulfonylimide anion represented by include the following. TIFF0007702806000140.tif33136

[0228] Examples of the sulfonylmethide anion include the following. TIFF0007702806000141.tif29123

[0229] Examples of the carboxylic acid anion include the following. TIFF0007702806000142.tif44155

[0230] Examples of the structural unit represented by formula (II-1-1) include the structural unit represented by the following, etc. When the resin (A) contains the structural unit (II), the content of the structural unit (II) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and still more preferably 3 to 10 mol% based on all the structural units of the resin (A).

[0231] The resin (A) may have structural units other than the above-mentioned structural units, and examples of such structural units include structural units well-known in the art.

[0232] The resin (A) is preferably a resin composed of the structural unit (a1) and the structural unit (s). The structural unit (a1) is preferably at least one selected from the group consisting of the structural unit (a1-0), the structural unit (a1-1), and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group), more preferably at least two kinds, and still more preferably the structural unit (a1-1) and / or the structural unit (a1-2). The structural unit (s) is preferably at least one selected from the group consisting of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit represented by the formula (a2-A) or a structural unit represented by the formula (a2-1). The structural unit (a3) is preferably at least one selected from the group consisting of a structural unit represented by the formula (a3-1), a structural unit represented by the formula (a3-2), and a structural unit represented by the formula (a3-4).

[0233] Each structural unit constituting the resin (A) may be used alone or in combination of two or more, and can be produced by a known polymerization method (for example, radical polymerization method) using monomers that lead to these structural units. The content of each structural unit of the resin (A) can be adjusted by the amount of monomers used in the polymerization. The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, still more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or less, still more preferably 15,000 or less). In this specification, the weight average molecular weight is a value determined by gel permeation chromatography under the conditions described in the examples.

[0234] <Resin other than resin (A)> The resist composition of the present invention may be used in combination with a resin other than the resin (A). Examples of the resin other than the resin (A) include resins containing the structural unit (a4) or the structural unit (a5) (hereinafter sometimes referred to as resin (X)). Among them, the resin containing the structural unit (a4) is preferable as the resin (X). In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, and still more preferably 45 mol% or more based on the total of all the structural units of the resin (X). 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. Among them, the resin (X) is preferably a resin composed of only the structural unit (a4) and / or the structural unit (a5), and more preferably a resin composed of only the structural unit (a4). Each structural unit constituting the resin (X) may be used alone or in combination of two or more, and can be produced by a known polymerization method (for example, radical polymerization method) using the monomers that induce these structural units. The content of each structural unit of the resin (X) can be adjusted by the amount of the monomers used in the polymerization. The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight average molecular weight of the resin (X) is the same as that of the resin (A). When the resist composition contains the resin (X), its content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, still more preferably 1 to 40 parts by mass, even more preferably 1 to 30 parts by mass, and particularly preferably 1 to 8 parts by mass with respect to 100 parts by mass of the resin (A).

[0235] The content rate of the resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less with respect to the solid content of the resist composition. When the resist composition contains a resin other than the resin (A), the total content rate of the resin (A) and the resin other than the resin (A) is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less with respect to the solid content of the resist composition. The solid content of the resist composition and the content rate of the resin with respect thereto can be measured by known analysis means such as liquid chromatography or gas chromatography.

[0236] <Solvent (E)> The content rate of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less, preferably 92% by mass or more and 99% by mass or less, more preferably 94% by mass or more and 99% by mass or less. The content rate of the solvent (E) can be measured by known analysis means such as liquid chromatography or gas chromatography. Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One kind of the solvent (E) may be used alone, or two or more kinds may be used.

[0237] <Quencher (C)> The quencher (C) includes a salt that generates an acid having a lower acidity than the acid generated from the basic nitrogen-containing organic compound or the acid generator (B) (however, excluding the carboxylate represented by the formula (I)). When the resist composition contains the quencher (C), the content of the quencher (C) is preferably about 0.01 to 15% by mass, more preferably about 0.01 to 10% by mass, still more preferably about 0.1 to 5% by mass, and even more preferably about 0.1 to 3% by mass, based on the solid content of the resist composition. Examples of the basic nitrogen-containing organic compound include amines and ammonium salts. Examples of the amines include aliphatic amines and aromatic amines. Examples of the aliphatic amines include primary amines, secondary amines, and tertiary amines. Examples of the amine include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridine, 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'-dipyridylsulfide, 4,4'-dipyridyldisulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. Aromatic amines such as diisopropylaniline are preferable, and 2,6-diisopropylaniline is more preferable. Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate, choline, and the like.

[0238] The acidity of a 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). A salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is a salt having an acid dissociation constant of the acid generated from the salt usually of -3 < pKa, preferably -1 < pKa < 7, and more preferably 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 salts represented by the following formula, salts represented by formula (D) described in JP-A-2015-147926 (hereinafter sometimes referred to as "weak acid inner salt (D)"), and salts described in JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-39502, and JP-A-2011-191745. Preferably, it is a salt that generates a carboxylic acid with a lower acidity than the acid generated from the acid generator (B) (a salt having a carboxylic acid anion), and more preferably, it is the weak acid inner salt (D). TIFF0007702806000144.tif97168

[0239] Examples of the weak acid inner salt (D) include the following salts. TIFF0007702806000145.tif72166

[0240] 〈Other components〉 The resist composition of the present invention may contain, if necessary, components other than the above-described components (hereinafter sometimes referred to as "other components (F)"). There are no particular limitations on the other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc. can be used.

[0241] 〈Preparation of Resist Composition〉 The resist composition of the present invention can be prepared by mixing a carboxylate (I), a resin (A), an acid generator (B), and, if necessary, a resin other than the resin (A), a solvent (E), a quencher (C), and other components (F). The mixing order is arbitrary and is not particularly limited. The temperature during mixing can be appropriately selected from 10 to 40 °C according to the type of resin, etc. and the solubility of the resin, etc. in the solvent (E). The mixing time can be appropriately selected from 0.5 to 24 hours according to the mixing temperature. Note that the mixing means is also not particularly limited, and stirring and mixing, etc. can be used. After mixing the respective components, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

[0242] 〈Method for Manufacturing Resist Pattern〉 The method for manufacturing a resist pattern of the present invention (1) A step of 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) A step of exposing the composition layer, (4) A step of heating the exposed composition layer, and (5) A step of developing the heated composition layer. To apply the resist composition onto a substrate, it can be performed by a commonly used apparatus such as a spin coater. Examples of the substrate include inorganic substrates such as silicon wafers. Before applying the resist composition, the substrate may be cleaned, or an antireflection film, etc. may be formed on the substrate. By drying the coated composition, the solvent is removed to form a composition layer. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-bake), or by using a decompression device. The heating temperature is preferably 50 to 200 °C, and the heating time is preferably 10 to 180 seconds. Also, the pressure during vacuum drying is preferably about 1 to 1.0×10 5 Pa. The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. As the exposure light source, those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), those that convert the laser light from a solid laser light source (such as YAG or semiconductor laser) into harmonic laser light in the far ultraviolet region or vacuum ultraviolet region and emit it, electron beams, those that irradiate extreme ultraviolet light (EUV), etc., various ones can be used. In this specification, irradiating these radiations may be collectively referred to as "exposure". During exposure, usually, exposure is performed through a mask corresponding to the required pattern. When the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask. The exposed composition layer is heat-treated (so-called post-exposure bake) to promote the deprotection reaction in the acid-labile group. The heating temperature is usually about 50 to 200 °C, preferably about 70 to 150 °C. The heated composition layer is usually developed using a developing solution with a developing device. Examples of the developing method include the dip method, paddle method, spray method, dynamic dispense method, etc. The developing temperature is preferably, for example, 5 to 60 °C, and the developing time is preferably, for example, 5 to 300 seconds. By selecting the type of developing solution as follows, a positive resist pattern or a negative resist pattern can be manufactured. When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be any of various alkaline aqueous solutions used in this field. For example, aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline) can be mentioned. The alkaline developer may contain a surfactant. After development, it is preferable to wash the resist pattern with ultrapure water and then remove the water remaining on the substrate and the pattern. When producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used as the developer. Examples of the organic solvent contained in the organic developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycol ether solvents such as propylene glycol monomethyl ether; amide solvents such as N,N-dimethylacetamide; and aromatic hydrocarbon solvents such as anisole. In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and even more preferably substantially only the organic solvent. Among them, as the organic developer, a developer containing butyl acetate and / or 2-heptanone is preferable. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably substantially only butyl acetate and / or 2-heptanone. The organic developer may contain a surfactant. Further, the organic developer may contain a trace amount of water. During development, the development may be stopped by substituting with a solvent of a different type from the organic developer. It is preferable to wash the developed resist pattern with a rinse solution. The rinse solution is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, preferably an alcohol solvent or an ester solvent. After washing, it is preferable to remove the rinse solution remaining on the substrate and the pattern.

[0243] <Usage> The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or a resist composition for EUV exposure, particularly as a resist composition for ArF excimer laser exposure, and is useful for semiconductor microfabrication.

Examples

[0244] The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or the amount used are based on mass unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography. The analysis conditions for gel permeation chromatography are as follows. Column: TSKgel Multipore HXL-M x 3 + guard column (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI detector Column temperature: 40 °C Injection volume: 100 μl Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation) The structure of the compound was confirmed by measuring the molecular ion peak using mass spectrometry (LC is Agilent model 1100, MASS is Agilent LC / MSD model). In the following examples, the value of this molecular ion peak is indicated by “MASS”.

[0245] Example 1: Synthesis of the salt represented by formula (I-857) 1.76 parts of the salt represented by TIFF0007702806000146.tif77148 formula (I-857-a), 2.20 parts of the compound represented by formula (I-857-b), and 20 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. To the resulting mixture, 0.88 part of potassium carbonate was added, and after stirring at 23°C for 30 minutes, the mixture was further stirred at 90°C for 3 hours to obtain a mixture containing the salt represented by formula (I-857-c). After cooling the resulting mixture to 23°C, 12 parts of a 5% aqueous oxalic acid solution was added and stirred at 23°C for 30 minutes, then 1.47 parts of the salt represented by formula (I-857-d) was added and stirred at 23°C for 7 hours. To the resulting reaction product, 30 parts of chloroform and 30 parts of ion-exchanged water were added, and after stirring at 23°C for 30 minutes, the layers were separated and the organic layer was taken out. To the obtained organic layer, 30 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the layers were separated and the organic layer was taken out. This water washing operation was repeated 6 times. By concentrating the obtained organic layer, 3.22 parts of the salt represented by formula (I-488) was obtained. MASS(ESI(+)Spectrum):M + 716.8 MASS(ESI(-)Spectrum):M - 193.1

[0246] Example 2: Synthesis of the salt represented by formula (I-859) 1.76 parts of the salt represented by formula (I-857-a), 2.20 parts of the compound represented by formula (I-857-b), and 20 parts of dimethylformamide were mixed and stirred at 23 °C for 30 minutes. To the resulting mixture, 0.88 part of potassium carbonate was added and stirred at 23 °C for 30 minutes, and then further stirred at 90 °C for 3 hours to obtain a mixture containing the salt represented by formula (I-857-c). After cooling the resulting mixture to 23 °C, 12 parts of a 5% aqueous oxalic acid solution was added and stirred at 23 °C for 30 minutes, and then 2.19 parts of the salt represented by formula (I-859-d) was added and stirred at 23 °C for 7 hours. To the resulting reaction product, 30 parts of chloroform and 30 parts of ion-exchanged water were added and stirred at 23 °C for 30 minutes, and then separated to extract the organic layer. To the obtained organic layer, 30 parts of ion-exchanged water was added and stirred at 23 °C for 30 minutes, and then separated to extract the organic layer. This water washing operation was repeated 6 times. By concentrating the obtained organic layer, 3.88 parts of the salt represented by formula (I-859) was obtained. MASS(ESI(+)Spectrum):M + 716.8 MASS(ESI(-)Spectrum):M - 337.1

[0247] Example 3: Synthesis of the salt represented by formula (I-954) 2.35 parts of the salt represented by formula (I-859-d), 2.72 parts of the salt represented by formula (I-954-a), 41 parts of chloroform, 12 parts of dimethylformamide, and 28 parts of methanol were mixed and stirred at 23 °C for 12 hours, and then separated to extract the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added and stirred at 23 °C for 30 minutes, and then separated to extract the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 3.39 parts of the salt represented by formula (I-954-b) was obtained. 1.71 parts of the salt represented by formula (I-954-b), 1.10 parts of the compound represented by formula (I-857-b), and 20 parts of acetonitrile were mixed and stirred at 23 °C for 30 minutes. To the resulting mixture, 0.44 parts of potassium carbonate was added, and after stirring at 23 °C for 30 minutes, it was further stirred at 60 °C for 12 hours. To the resulting reaction product, 40 parts of chloroform and 20 parts of ion-exchanged water were added, and after stirring at 23 °C for 30 minutes, the layers were separated and the organic layer was taken out. To the obtained organic layer, 20 parts of ion-exchanged water was added, and after stirring at 23 °C for 30 minutes, the layers were separated and the organic layer was taken out. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 2.24 parts of the salt represented by formula (I-954) was obtained. MASS(ESI(+)Spectrum):M + 744.9 MASS(ESI(-)Spectrum):M - 337.1

[0248] Example 4: Synthesis of the salt represented by formula (I-1714) 3.80 parts of the compound represented by TIFF0007702806000150.tif38155 (I-1714-a) and 6.40 parts of Oxone® were mixed, stirred at 23 °C for 30 minutes, and then cooled to 5 °C. After adding 23.56 parts of sulfuric acid to the resulting mixture, it was stirred at 5 °C for 30 minutes. To the resulting mixture, a mixed solution of 3.68 parts of the compound represented by formula (I-1714-b) and 18.40 parts of chloroform was added, stirred at 5 °C for 30 minutes, and then further stirred at 23 °C for 2 hours. The resulting mixed solution was added to 120 parts of methanol, stirred at 23 °C for 30 minutes, and then filtered. After concentrating the obtained filtrate, 125 parts of chloroform and 25 parts of acetonitrile were added to the concentrated residue, stirred at 23 °C for 30 minutes, 60 parts of 5% hydrochloric acid was added, stirred at 23 °C for 30 minutes, and then the layers were separated to obtain the organic layer. 40 parts of ion-exchanged water was added to the obtained organic layer, stirred at 23 °C for 30 minutes, and then the layers were separated to obtain the organic layer. This water washing operation was repeated 3 times. The obtained organic layer was concentrated, 45 parts of tert-butyl methyl ether was added to the concentrated mixture, stirred at 23 °C for 30 minutes, and then filtered to obtain 2.37 parts of the salt represented by formula (I-1714-c). 2.32 parts of the salt represented by JPEG0007702806000151.jpg34165 (I-859-d), 30 parts of chloroform and 27 parts of 5% aqueous oxalic acid solution were mixed and stirred at 23 °C for 30 minutes. To the resulting mixed solution, 2.14 parts of the salt represented by formula (I-1714-c) was added, stirred at 23 °C for 1 hour, and then the layers were separated to obtain the organic layer. By concentrating the obtained organic layer, 3.44 parts of the salt represented by formula (I-1714-d) was obtained. 1.77 parts of the salt represented by formula (I-1714-d), 0.55 parts of the compound represented by formula (I-857-b), and 20 parts of acetonitrile were mixed and stirred at 23 °C for 30 minutes. To the resulting mixture, 0.22 parts of potassium carbonate was added, and after stirring at 23 °C for 30 minutes, it was further stirred at 60 °C for 12 hours. To the resulting reaction product, 40 parts of chloroform and 20 parts of ion-exchanged water were added, and after stirring at 23 °C for 30 minutes, the layers were separated and the organic layer was taken out. To the obtained organic layer, 20 parts of ion-exchanged water was added, and after stirring at 23 °C for 30 minutes, the layers were separated and the organic layer was taken out. This washing operation with water was repeated 5 times. By concentrating the obtained organic layer, 1.99 parts of the salt represented by formula (I-1714) was obtained. MASS(ESI(+)Spectrum):M + 569.0 MASS(ESI(-)Spectrum):M - 337.1

[0249] Example 5: Synthesis of the salt represented by formula (I-3329) 12 parts of potassium iodate, 18.53 parts of the compound represented by formula (I-3329-a), 24 parts of acetic acid and 18 parts of acetic anhydride were mixed and stirred at 23 °C for 30 minutes, and then cooled to 5 °C. To the resulting mixture, 12 parts of sulfuric acid was added over 10 minutes, and after stirring at 5 °C for 3 hours, it was further stirred at 23 °C for 12 hours. To the resulting mixed solution, 36 parts of tert-butyl methyl ether and 36 parts of ion-exchanged water were added, and after stirring at 23 °C for 2 hours, it was filtered. To the obtained filtrate, a mixed solution of 6 parts of sodium bromide and 30 parts of ion-exchanged water was added, and after stirring at 23 °C for 2 hours, it was filtered to obtain 15.69 parts of the salt represented by formula (I-3329-b). 2.35 parts of the salt represented by formula (I-859-d), 2.72 parts of the salt represented by formula (I-3329-d), 41 parts of chloroform, 12 parts of dimethylformamide and 28 parts of methanol were mixed and stirred at 23 °C for 12 hours, then separated to obtain the organic layer. 20 parts of ion-exchanged water was added to the obtained organic layer and stirred at 23 °C for 30 minutes, then separated to obtain the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 3.13 parts of the salt represented by formula (I-3329-d) was obtained. 1.71 parts of the salt represented by formula (I-3329-d), 1.10 parts of the compound represented by formula (I-857-b) and 20 parts of acetonitrile were mixed and stirred at 23 °C for 30 minutes. 0.44 part of potassium carbonate was added to the obtained mixture and stirred at 23 °C for 30 minutes, then further stirred at 60 °C for 12 hours. 40 parts of chloroform and 20 parts of ion-exchanged water were added to the obtained reaction product and stirred at 23 °C for 30 minutes, then separated to obtain the organic layer. 20 parts of ion-exchanged water was added to the obtained organic layer and stirred at 23 °C for 30 minutes, then separated to obtain the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 2.21 parts of the salt represented by formula (I-3329) was obtained. MASS(ESI(+)Spectrum):M + 744.9 MASS(ESI(-)Spectrum):M - 337.1

[0250] Example 6: Synthesis of the salt represented by formula (I-3139) 3.80 parts of the compound represented by formula (I-3139-a) and 6.40 parts of Oxone® were mixed and stirred at 23 °C for 30 minutes, and then cooled to 5 °C. To the resulting mixture, 23.56 parts of sulfuric acid was added, and the mixture was stirred at 5 °C for 30 minutes. To the resulting mixture, a mixed solution of 3.68 parts of the compound represented by formula (I-1714-b) and 18.40 parts of chloroform was added, and the mixture was stirred at 5 °C for 30 minutes and then further stirred at 23 °C for 2 hours. The resulting mixed solution was added to 120 parts of methanol, stirred at 23 °C for 30 minutes, and then filtered. The resulting filtrate was concentrated, and to the concentrated residue, 125 parts of chloroform and 25 parts of acetonitrile were added. After stirring at 23 °C for 30 minutes, 60 parts of 5% hydrochloric acid was added and the mixture was stirred at 23 °C for 30 minutes, and then the layers were separated to obtain the organic layer. 40 parts of ion-exchanged water was added to the obtained organic layer, stirred at 23 °C for 30 minutes, and then the layers were separated to obtain the organic layer. This water washing operation was repeated 3 times. The obtained organic layer was concentrated, 45 parts of tert-butyl methyl ether was added to the concentrated mixture, stirred at 23 °C for 30 minutes, and then filtered to obtain 3.32 parts of the salt represented by formula (I-3139-c). 2.32 parts of the salt represented by formula (I-859-d), 30 parts of chloroform and 27 parts of 5% aqueous oxalic acid solution were mixed and stirred at 23 °C for 30 minutes. To the resulting mixture, 2.14 parts of the salt represented by formula (I-3139-c) was added, and the mixture was stirred at 23 °C for 1 hour, and then the layers were separated to obtain the organic layer. By concentrating the obtained organic layer, 3.09 parts of the salt represented by formula (I-3139-d) was obtained. 1.77 parts of the salt represented by formula (I-3139-d), 0.55 part of the compound represented by formula (I-857-b) and 20 parts of acetonitrile were mixed and stirred at 23 °C for 30 minutes. To the resulting mixture, 0.22 part of potassium carbonate was added, and the mixture was stirred at 23 °C for 30 minutes, and then further stirred at 60 °C for 12 hours. To the resulting reaction product, 40 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23 °C for 30 minutes, and then separated to obtain the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23 °C for 30 minutes, and then separated to obtain the organic layer. This washing operation with water was repeated 5 times. By concentrating the obtained organic layer, 1.89 parts of the salt represented by formula (I-3139) was obtained. MASS(ESI(+)Spectrum):M + 569.0 MASS(ESI(-)Spectrum):M - 337.1

[0251] Example 7: Synthesis of the salt represented by formula (I-3424) 12 parts of potassium iodate, 21.56 parts of the compound represented by formula (I-3424-a), 24 parts of acetic acid and 18 parts of acetic anhydride were mixed and stirred at 23 °C for 30 minutes, and then cooled to 5 °C. To the resulting mixture, 12 parts of sulfuric acid was added over 10 minutes, and the mixture was stirred at 5 °C for 3 hours, and then further stirred at 23 °C for 12 hours. To the resulting mixed solution, 36 parts of tert-butyl methyl ether and 36 parts of ion-exchanged water were added, and the mixture was stirred at 23 °C for 2 hours, and then filtered. To the obtained filtrate, a mixed solution of 6 parts of sodium bromide and 30 parts of ion-exchanged water was added, and the mixture was stirred at 23 °C for 2 hours, and then filtered to obtain 16.42 parts of the salt represented by formula (I-3424-b). 2.35 parts of the salt represented by formula (I-859-d), 2.46 parts of the salt represented by formula (I-3424-b), 41 parts of chloroform, 12 parts of dimethylformamide and 28 parts of methanol were mixed and stirred at 23 °C for 12 hours, then separated to obtain the organic layer. 20 parts of ion-exchanged water was added to the obtained organic layer and stirred at 23 °C for 30 minutes, then separated to obtain the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 3.86 parts of the salt represented by formula (I-3424-d) was obtained. 1.79 parts of the salt represented by formula (I-3424-d), 2.20 parts of the compound represented by formula (I-857-b) and 20 parts of acetonitrile were mixed and stirred at 23 °C for 30 minutes. 0.88 part of potassium carbonate was added to the obtained mixture and stirred at 23 °C for 30 minutes, then further stirred at 60 °C for 12 hours. 40 parts of chloroform and 20 parts of ion-exchanged water were added to the obtained reaction product and stirred at 23 °C for 30 minutes, then separated to obtain the organic layer. 20 parts of ion-exchanged water was added to the obtained organic layer and stirred at 23 °C for 30 minutes, then separated to obtain the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.96 parts of the salt represented by formula (I-3424) was obtained. MASS(ESI(+)Spectrum):M + 1180.7 MASS(ESI(-)Spectrum):M - 337.1

[0252] Example 8: Synthesis of the salt represented by formula (I-3044) 1.77 parts of the salt represented by TIFF0007702806000162.tif64138 (I-1714-d), 0.41 part of the compound represented by formula (I-3044-b), and 20 parts of acetonitrile were mixed and stirred at 23 °C for 30 minutes. To the resulting mixture, 0.22 part of potassium carbonate was added, and after stirring at 23 °C for 30 minutes, it was further stirred at 60 °C for 12 hours. To the resulting reaction product, 40 parts of chloroform and 20 parts of ion-exchanged water were added, and after stirring at 23 °C for 30 minutes, the layers were separated and the organic layer was taken out. To the obtained organic layer, 20 parts of ion-exchanged water were added, and after stirring at 23 °C for 30 minutes, the layers were separated and the organic layer was taken out. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.86 parts of the salt represented by formula (I-3044) were obtained. MASS(ESI(+)Spectrum):M + 511.1 MASS(ESI(-)Spectrum):M - 337.1

[0253] Example 9: Synthesis of the salt represented by formula (I-3614) 1.77 parts of the salt represented by TIFF0007702806000163.tif62133 (I-1714-d), 0.90 part of the compound represented by formula (I-3614-b), and 20 parts of acetonitrile were mixed and stirred at 23 °C for 30 minutes. To the resulting mixture, 0.22 part of potassium carbonate was added, and after stirring at 23 °C for 30 minutes, it was further stirred at 60 °C for 12 hours. To the resulting reaction product, 40 parts of chloroform and 20 parts of ion-exchanged water were added, and after stirring at 23 °C for 30 minutes, the layers were separated and the organic layer was taken out. To the obtained organic layer, 20 parts of ion-exchanged water were added, and after stirring at 23 °C for 30 minutes, the layers were separated and the organic layer was taken out. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 2.32 parts of the salt represented by formula (I-3614) were obtained. MASS(ESI(+)Spectrum):M + 710.9 MASS(ESI(-)Spectrum):M - 337.1

[0254] Example 10: Synthesis of the salt represented by formula (I-3709) 1.77 parts of the salt represented by formula (I-1714-d), 0.90 parts of the compound represented by formula (I-3709-b), and 20 parts of acetonitrile were mixed and stirred at 23°C for 30 minutes. To the resulting mixture, 0.22 parts of potassium carbonate was added, and after stirring at 23°C for 30 minutes, the mixture was further stirred at 60°C for 12 hours. To the resulting reaction product, 40 parts of chloroform and 20 parts of ion-exchanged water were added, and after stirring at 23°C for 30 minutes, the layers were separated and the organic layer was taken out. To the obtained organic layer, 20 parts of ion-exchanged water was added, and after stirring at 23°C for 30 minutes, the layers were separated and the organic layer was taken out. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 2.28 parts of the salt represented by formula (I-3709) was obtained. MASS(ESI(+)Spectrum):M + 710.9 MASS(ESI(-)Spectrum):M - 337.1

[0255] Synthesis of resin The compounds (monomers) used for the synthesis of resin (A) are shown below. Hereinafter, these compounds are referred to as "monomer (a1-1-3)" etc. according to their formula numbers. TIFF0007702806000165.tif46154

[0256] Synthesis Example 1 [Synthesis of Resin A1] As monomers, monomer (a1-4-2), monomer (a1-1-3) and monomer (a1-2-6) were used and mixed so that their molar ratio [monomer (a1-4-2): monomer (a1-1-3): monomer (a1-2-6)] was 38:24:38. Further, 1.5 times the mass of methyl isobutyl ketone was mixed with this monomer mixture based on the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% based on the total number of moles of all monomers, and polymerization was carried out by heating this at 85 °C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid (2.5 wt%) 2.0 times the mass of all monomers was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was obtained by filtration and recovery, and the weight average molecular weight was about 5.3×10 3 Resin A1 (copolymer) with a yield of 78% was obtained. This resin A1 has the following structural units. TIFF0007702806000166.tif30126

[0257] Synthesis Example 2 [Synthesis of Resin A2] As monomers, monomer (a1-4-2) and monomer (a1-2-6) were used and mixed so that their molar ratio [monomer (a1-4-2): monomer (a1-2-6)] was 38:62. Further, 1.5 times the mass of methyl isobutyl ketone was mixed with this monomer mixture based on the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% based on the total number of moles of all monomers, and polymerization was carried out by heating this at 85 °C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid (2.5 wt%) 2.0 times the mass of all monomers was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was obtained by filtration and recovery, and the weight average molecular weight was about 5.4×10 3 Resin A2 (copolymer) with a yield of 89% was obtained. This resin A2 has the following structural units. TIFF0007702806000167.tif2887

[0258] Synthesis Example 3 [Synthesis of Resin A3] As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2) and monomer (aa1-4-2) were used, and their molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-2)] was mixed so as to be in a ratio of 20:35:3:15:27. Further, to this monomer mixture, methyl isobutyl ketone 1.5 times the total mass of all monomers was mixed. To the obtained mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators in amounts of 1.2 mol% and 3.6 mol%, respectively, based on the total monomer amount, and these were heated at 73 °C for about 5 hours. Thereafter, to the polymerization reaction solution, an aqueous solution of p-toluenesulfonic acid (2.5 wt%) 2.0 times the total mass of all monomers was added, stirred for 12 hours, and then separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was obtained by filtration and recovery. The resin A3 having a weight average molecular weight of about 5.3×10 3 was obtained in a yield of 63%. This resin A3 has the following structural units. TIFF0007702806000168.tif38154

[0259] Synthesis Example 4 [Synthesis of Resin A4] As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2) and monomer (a1-4-13) were used, and their molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-13)] was mixed so as to be in a ratio of 20:35:3:15:27. Further, to this monomer mixture, methyl isobutyl ketone 1.5 times the total mass of all monomers was mixed. To the obtained mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, based on the total monomer amount, and these were heated at 73 °C for about 5 hours. Then, to the polymerization reaction solution, an aqueous p-toluenesulfonic acid solution (2.5 wt%) 2.0 times the total mass of all monomers was added, stirred for 12 hours, and then liquid-separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was filtered and recovered to obtain resin A4 having a weight average molecular weight of about 5.1×10 3 and having a yield of 61%. This resin A4 has the following structural units. TIFF0007702806000169.tif38154

[0260] <Preparation of resist composition> As shown in Table 2, the following components were mixed, and the obtained mixture was filtered through a fluororesin filter with a pore size of 0.2 μm to prepare a resist composition.

Table 2

[0261] <Resin> A1 to A4: Resin A1 to Resin A4 <Acid generator (B)> B1-25: Salt represented by formula (B1-25); synthesized by the method described in JP-A-2011-126869 TIFF0007702806000171.tif2667<Carboxylate (I)> I-857: Salt represented by formula (I-857) I-859: Salt represented by formula (I-859) I-954: Salt represented by formula (I-954) I-1714: Salt represented by formula (I-1714) I-3044: Salt represented by formula (I-3044) I-3139: Salt represented by formula (I-3139) I-3329: Salt represented by formula (I-3329) I-3424: Salt represented by formula (I-3424) I-3614: Salt represented by formula (I-3614) I-3709: Salt represented by formula (I-3709) <Quencher (C)> IX-1 IX-2 IX-3 TIFF0007702806000172.tif58138 <Solvent> 400 parts of propylene glycol monomethyl ether acetate 100 parts of propylene glycol monomethyl ether 5 parts of γ-butyrolactone

[0262] (Electron Beam Exposure Evaluation of Resist Composition: Alkaline Development) A 6-inch silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90 °C for 60 seconds. The resist composition was spin-coated on this silicon wafer so that the film thickness of the composition layer was 0.04 μm. Then, it was prebaked on a direct hot plate at the temperature shown in the "PB" column of Table 2 for 60 seconds to form a composition layer. A line and space pattern (pitch 60 nm / line width 30 nm) was directly drawn on the composition layer formed on the wafer using an electron beam lithography machine ["ELS-F125 125 keV" manufactured by Elionix, Inc.] while changing the exposure dose step by step. After exposure, post-exposure baking was performed on a hot plate at the temperature shown in the "PEB" column of Table 2 for 60 seconds, and then paddle development was performed for 60 seconds with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to obtain a resist pattern. The obtained resist pattern (line and space pattern) was observed with a scanning electron microscope, and the exposure amount at which the line width and space width of the line and space pattern with a pitch of 60 nm became 1:1 was defined as the effective sensitivity.

[0263] Line edge roughness evaluation (LER): The amplitude of the unevenness of the side wall surface of the resist pattern manufactured with the effective sensitivity was measured with a scanning electron microscope to determine the line edge roughness. The results are shown in Table 3.

Table 3

[0264] (Electron beam exposure evaluation of resist composition: organic solvent development) A 6-inch silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90 °C for 60 seconds. The resist composition was spin-coated on this silicon wafer so that the film thickness of the composition layer became 0.04 μm. Then, pre-baking was performed on a direct hot plate at the temperature shown in the "PB" column of Table 2 for 60 seconds to form a composition layer. Using an electron beam writer ["ELS-F125 125 keV" manufactured by Elionix, Inc.] on the composition layer formed on the wafer, the exposure amount was changed stepwise, and direct drawing was performed so as to obtain a line and space pattern (pitch 60 nm / line width 30 nm) after development. After exposure, post-exposure baking was performed on a hot plate at the temperature shown in the "PEB" column of Table 2 for 60 seconds. Next, the composition layer on this silicon wafer was developed by the dynamic dispense method at 23 °C for 20 seconds using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as the developer to obtain a resist pattern. The obtained resist pattern (line and space pattern) was observed with a scanning electron microscope, and the exposure dose at which the line width and space width of the line and space pattern with a pitch of 60 nm were 1:1 was defined as the effective sensitivity.

[0265] Line edge roughness evaluation (LER): The fluctuation width of the unevenness on the side wall surface of the resist pattern manufactured with the effective sensitivity was measured with a scanning electron microscope to obtain the line edge roughness. The results are shown in Table 4.

Table 4

Industrial Applicability

[0266] The resist composition containing the carboxylate of the present invention can obtain a resist pattern having good line edge roughness (LER), and thus is suitable for fine processing of semiconductors and extremely useful industrially.

Claims

1. A carboxylate represented by formula (I). [In formula (I), R １ and R ２ each independently represents an iodine atom, a fluorine atom, or an alkyl fluoride group having 1 to 6 carbon atoms. R ４ , R ５ , R ７ and R ８ each independently represents a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and -CH 2 - in the haloalkyl group and the alkyl group may be replaced by -O-, -CO-, -S- or -SO ２ -. X １ and X ２ each independently represents an oxygen atom or a sulfur atom. m1 represents an integer of any one of 1 to 5, and when m1 is 2 or more, the groups in a plurality of parentheses may be the same as or different from each other. m2 represents an integer of any one of 0 to 5, and when m2 is 2 or more, the groups in a plurality of parentheses may be the same as or different from each other. m4 represents any integer from 0 to 4, and when m4 is 2 or more, the plurality of Rs ４ may be the same as or different from each other. m5 represents any integer from 0 to 4. When m5 is 2 or more, the plurality of Rs ５ may be the same as or different from each other. m7 represents any integer from 0 to 4, and when m7 is 2 or more, the plurality of Rs ７ may be the same as or different from each other. m8 represents any integer from 0 to 5, and when m8 is 2 or more, the plurality of Rs ８ may be the same as or different from each other. However, 1 ≤ m1 + m7 ≤ 5 and 0 ≤ m2 + m8 ≤ 5. X ０ represents a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, and -CH 2 - in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO ２ -.]

2. X １ and X ２ The carboxylate according to claim 1, wherein X and X are oxygen atoms.

3. m1 is 1 or 2, The carboxylate according to claim 1 or 2, wherein m2 is 0, 1 or 2.

4. X １ and X ２ The bonding position of ＋ is bonded to the p-position or m-position with respect to the bonding position of I, and the carboxylate according to any one of claims 1 to 3.

5. R ４ or R ５ represents an iodine atom, a fluorine atom, a trifluoromethyl group, or a hydroxy group, the carboxylate according to any one of claims 1 to 4.

6. m4 is 2, Two Rs ４ wherein one of them is an iodine atom, a fluorine atom or a trifluoromethyl group and the other is a hydroxy group, the carboxylate according to any one of claims 1 to 5.

7. m2 is 0, m8 is 1, and R ８ is a branched alkyl group having 3 or 4 carbon atoms, the carboxylate according to any one of claims 1 to 6.

8. The carboxylate according to any one of claims 1 to 6, wherein m1 and m2 are each 1 or m1 and m2 are each 2.

9. X ０ is an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (however, -CH 2 - contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO ２ -).) Or the carboxylate according to any one of claims 1 to 8, which is an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent.

10. X ０ is an alicyclic hydrocarbon group which may have a fluorine atom or a hydroxy group (wherein -CH 2 - included in the alicyclic hydrocarbon group may be replaced by -O- or -CO-), or an aromatic hydrocarbon group which may have a halogen atom, a hydroxy group or a C1-C4 perfluoroalkyl group. The carboxylate according to any one of claims 1 to 9.

11. X ０ The carboxylate according to any one of claims 1 to 10, wherein X is a group represented by the formula (aa). [In formula (aa), X a and X b each independently represents -O- or -S-. X １ａ represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and the -CH 2 - in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO ２ -. X ２ａ represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, and the -CH 2 - in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO ２ -. * represents the bonding position with the carbon atom of -COO － .

12. A carboxylic acid generator containing the carboxylate according to any one of claims 1 to 11.

13. A resist composition containing the carboxylic acid generator according to claim 12, an acid generator other than the carboxylic acid generator, and a resin having an acid-labile group.

14. The resist composition according to claim 13, wherein the resin having an acid-labile group contains at least one selected from the group consisting 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 each independently represents -O- or *-O-(CH ２ ) k1 -CO-O-, k1 represents any integer from 1 to 7, and * represents a bond with -CO-. R a4 and R a5 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. m1 represents an integer of any one of 0 to 14. n1 represents an integer of any one of 0 to 10. n1' represents an integer of any one of 0 to 3.]

15. The resist composition according to claim 13 or 14, wherein the resin having an acid-labile group contains a structural unit represented by formula (a2-A). [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 alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 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 represents a single bond or ＊ -X a51 -(A a52 -X a52 ) nｂ -, where * represents a bond with the carbon atom to which -R a50 is attached. 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 any one of 0 to 4. When mb is any integer of 2 or more, the plurality of Rs a51 may be the same as or different from each other.]

16. (1) A step of applying the resist composition according to any one of claims 13 to 15 onto a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the exposed composition layer, and (5) A step of developing the heated composition layer, A method for manufacturing a resist pattern including these steps.

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