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

Abstract

To provide a carboxylate that makes it possible to produce a resist pattern having excellent line edge roughness (LER), a carboxylic acid generator, a resin and a resist composition comprising the same.SOLUTION: The present invention discloses a carboxylate represented by, for example, formula (I-2).SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Patent Document 1 describes a resist composition containing a resin containing a structural unit derived from a carboxylate represented by the following formula. TIFF0007691875000001.tif3449

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] 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 carboxylate and / or a resin containing a structural unit derived from the above carboxylate.

Means for Solving the Problems

[0005] The present invention includes the following inventions. [1] A carboxylate represented by formula (I). TIFF0007691875000002.tif79104[In formula (I), R 1 、R 2 and R 3 each independently represent a group represented by formula (4a). R 4 、R 5 、R 6 、R 7 、R8 and R 9 each independently represents a halogen atom, a hydroxy group, a C1-C12 fluoroalkyl group or a C1-C18 hydrocarbon group, and the hydrocarbon group may have a substituent, and the -CH 2 - in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -. X 1 , X 2 and X 3 each independently represents an oxygen atom or a sulfur atom. m1 represents any integer from 0 to 5, and when m1 is 2 or more, the groups in the plurality of parentheses may be the same as or different from each other. m2 represents any integer from 0 to 4, and when m2 is 2 or more, the groups in the plurality of parentheses may be the same as or different from each other. m3 represents any integer from 0 to 4, and when m3 is 2 or more, the groups in the 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 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 plurality of R 5 may be the same as or different from each other. m6 represents any integer from 0 to 4, and when m6 is 2 or more, the plurality of R 6 may be the same as or different from each other. m7 represents any integer from 0 to 5, and when m7 is 2 or more, the plurality of R 7 may be the same as or different from each other. m8 represents any integer from 0 to 4, and when m8 is 2 or more, the plurality of R 8 may be the same as or different from each other. m9 represents any integer from 0 to 4, and when m9 is 2 or more, the plurality of R 9 may be the same as or different from each other. However, 0 ≦ m1 + m7 ≦ 5, 0 ≦ m2 + m8 ≦ 4, 0 ≦ m3 + m9 ≦ 4, and At least one of m1, m2, and m3 represents an integer of 1 or more. X 4 represents a single bond, -CH 2 -, -O-, -S-, -CO-, -SO- or -SO 2 -. 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 -. TIFF0007691875000003.tif4145[In formula (4a), R 10 represents a hydrogen atom or a methyl group. X 10 represents a bond type selected from the group consisting of an ether bond, an ester bond and a carbonate bond, or a linking group in which at least one or two bond types selected from the group consisting of an ether bond, an ester bond and a carbonate bond are combined with an aryl group. *10 represents the bonding site with the benzene ring. [2]X 1 , X 2 and X 3 are oxygen atoms, the carboxylate salt according to [1]. [3]X 10 is a group represented by any one of formula (X 1 -1) to formula (X 1 -7), the carboxylate salt according to [1] or [2]. TIFF0007691875000004.tif45141[In formula (X 1 -1) to formula (X 1 -7), *, ** are bonding sites, and ** is the bonding site with L 10 . L 10 represents a single bond or a hydrocarbon group having 1 to 36 carbon atoms which may have a substituent, and -CH 2 - in the hydrocarbon group may be replaced by -O-, -S-, -SO 2 - or -CO-. [4]X10 is a group represented by any of the formula (X 1 -1), the formula (X 1 -4) and the formula (X 1 -5) [3] The carboxylate described. [5] L 10 is a single bond or an alkanediyl group having 1 to 4 carbon atoms (provided that -CH 2 - contained in the alkanediyl group may be replaced by -O- or -CO-).) The carboxylate according to any one of [1] to [4]. [6] m1 is 1 or 2, m4 is 1 or 2, R 4 is a halogen atom [1] to [5] The carboxylate according to any one of. [7] m2 and m3 are 0, m8 and m9 are 1, R 8 and R 9 are each independently a halogen atom or an alkyl fluoride group having 1 to 6 carbon atoms, [1] to [6] The carboxylate according to any one of. [8] X 0 is an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (provided that -CH 2 - contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -).) Or an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent [1] to [7] The carboxylate according to any one of. [9] X 0 is an alicyclic hydrocarbon group having 3 to 36 carbon atoms which may have a fluorine atom or a hydroxy group (the -CH 2 - contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -).) Or an aromatic hydrocarbon group which may have a halogen atom, a hydroxy group or a perfluoroalkyl group having 1 to 4 carbon atoms [1] to [8] The carboxylate according to any one of.

[10] X 0 is a group represented by the formula (aa), [1] to [9] The carboxylate according to any one of. TIFF0007691875000005.tif2737 [In the 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 -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 -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 - . A carboxylic acid generator containing the carboxylate salt according to any one of

[11] [1] to

[10] . A resin containing a structural unit derived from the carboxylate salt according to any one of

[12] [1] to

[10] . The resin according to

[12] , further comprising a structural unit having an acid-labile group. A resist composition containing the carboxylic acid generator according to

[11] , an acid generator other than the carboxylic acid generator, and a resin having an acid-labile group. A resist composition containing the resin according to

[13] and an acid generator. In the resist composition according to

[14] or

[15] , the resin containing a structural unit having an acid-labile group contains at least one selected from the group consisting of the structural unit represented by formula (a1-1) and the structural unit represented by formula (a1-2). TIFF0007691875000006.tif4291[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 an integer of any one of 1 to 7, and * represents a bond with -CO. R a4 and R a5Each 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.

[17] A resist composition according to any one of

[14] to

[16] , wherein the resin containing a structural unit having an acid-labile group contains a structural unit represented by formula (a2-A). TIFF0007691875000007.tif4653 [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 -, and * represents a 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 a52 Each independently represents -O-, -CO-O-, or -O-CO-. nb represents 0 or 1. mb represents an 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.]

[18] A step of applying the resist composition according to any one of

[14] to

[17] 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.

Advantages of the Invention

[0006] By using the resist composition using the carboxylate of the present invention, a resist pattern can be manufactured with good line edge roughness (LER).

Embodiments for Carrying Out the Invention

[0007] 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 represent the same meaning. Among the groups described in this specification, those that can take both a linear structure and a branched structure may be either of them. When -CH 2 - in a hydrocarbon group or the like is replaced by -O-, -S-, -CO- or -SO 2 -, the same examples shall apply to each group. The “combined group” means a group formed by bonding two or more of the exemplified groups, and the valences of those groups may be appropriately changed depending on the bonding form. “Derived from” or “induced from” means 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.

[0008] [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)". TIFF0007691875000008.tif72164[In the formula, all symbols have the same meanings as described above.]

[0009] In formula (I), X 10 When it is a linking group in which one or two linking species selected from the group consisting of an ether bond, an ester bond, and a carbonate ester bond are combined with an aryl group, it is preferably a linking group represented by the following formula (X10). TIFF0007691875000009.tif4353In formula (X10), Ax represents a linking species that binds to L 10 and represents one linking species selected from the group consisting of a single bond, an ether bond, an ester bond, and a carbonate ester bond. Ay represents a linking species that binds to the carbon atom to which R 10 is bonded. When Ax is a single bond, Ay represents one selected from the group consisting of an ether bond, an ester bond, and a carbonate ester bond. When Ax is one linking species selected from the group consisting of an ether bond, an ester bond, and a carbonate ester, Ay represents one linking species selected from the group consisting of a single bond, an ether bond, an ester bond, and a carbonate ester bond. Rx represents a halogen atom, a hydroxy group, a fluorinated alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Among them, a fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, and an ethyl group are preferable. mx represents any integer from 0 to 4, and 0, 1, or 2 is preferable. When mx is an integer of 2 or more, the plurality of Rx may be the same as or different from each other. The bonding position of Ay in the aryl group is preferably the m-position or p-position relative to Ax, and more preferably the p-position. X 10 Specific examples of are the groups represented by the following formulas (X 1 -1) to formula (X 1 -14). TIFF0007691875000010.tif80141Among them, the groups represented by formula (X 1 -1) to formula (X 1 -7) are preferred, and the group represented by formula (X 1 -1), the group represented by formula (X 1 -3), the group represented by formula (X 1 -4) or the group represented by formula (X 1 -5) are more preferred, and R 10 is bonded to the carbon atom to which it is bonded via -CO-O- and is represented by formula (X 1 -1), the group represented by formula (X 1 -4) or the group represented by formula (X 1 -5) are even more preferred, and the group represented by formula (X 1 -1) or the group represented by formula (X 1 -4) are even more preferred.

[0010] L 10 Examples of the divalent hydrocarbon group having 1 to 36 carbon atoms for include divalent aliphatic hydrocarbon groups (divalent chain hydrocarbon groups such as alkanediyl groups, alkenediyl groups, alkynediyl groups, and divalent alicyclic hydrocarbon groups), divalent aromatic hydrocarbon groups, etc. A divalent hydrocarbon group formed by combining two or more of these groups may also be used.

[0011] Examples 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, 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; Examples of the branched alkanediyl group include 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. Examples of the alkenediyl group include an ethenediyl group, a propenediyl group, an isopropenediyl group, a butenediyl group, an isobutenediyl group, a tert-butenediyl group, a pentenediyl group, a hexenediyl group, a heptenediyl group, an octenediyl group, an isooctenediyl group, a nonenediyl group. Examples of the alkynediyl group include an ethynediyl group, a propynediyl group, an isopropynediyl group, a butynediyl group, an isobutynediyl group, a tert-butynediyl group, a pentynediyl group, a hexynediyl group, an octynediyl group, a nonynediyl group, and the like. The number of carbon atoms of the chain hydrocarbon group is preferably 1 to 12, more preferably 1 to 9, still more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. The divalent alicyclic hydrocarbon group may be monocyclic, polycyclic or spirocyclic. Examples of the divalent alicyclic hydrocarbon group include the groups represented below. The bonding site can be at any position. TIFF0007691875000011.tif41165Specifically, examples of the monocyclic divalent alicyclic hydrocarbon group include monocyclic cycloalkanediyl groups such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cyclohexene-3,6-diyl group, a cyclooctane-1,5-diyl group, and the like. Examples of the polycyclic divalent alicyclic hydrocarbon group include polycyclic cycloalkanediyl groups such as a norbornane-1,4-diyl group, a norbornane-2,5-diyl group, a 5-norbornene-2,3-diyl group, an adamantane-1,5-diyl group, an adamantane-2,6-diyl group, and the like. The number of carbon atoms in the divalent alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 16, and still more preferably 3 to 12. Examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, an anthrylene group, a biphenylene group, a phenanthrylene group, etc. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10. Examples of the hydrocarbon group formed by combining two or more types include a group formed by combining an alkanediyl group with an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group, such as -alicyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-alicyclic hydrocarbon group-, -alkanediyl group-alicyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-aromatic hydrocarbon group-, -aromatic hydrocarbon group-alkanediyl group-, etc.

[0012] L 10 The -CH 2 - in the hydrocarbon group having 1 to 36 carbon atoms of 2 L may be replaced by -O-, -S-, -CO- or -SO L 10 When the hydrocarbon group having 1 to 36 carbon atoms of 2 L has a substituent or the -CH 2 - in the hydrocarbon group is replaced by -O-, -S-, -CO- or -SO -, the number of carbon atoms before replacement is taken as the number of carbon atoms of the hydrocarbon group. 2 The -CH 2 - in the hydrocarbon group being replaced by -O-, -S-, -SO 2 - or -CO- includes a hydroxy group (the group in which -CH 2 - in the methyl group is replaced by -O-), a carboxy group (the group in which -CH 2 -CH 2 - in the ethyl group is replaced by -O-CO-), a thiol group (the group in which -CH 2 ​​- is a group replaced by -O-, an alkoxycarbonyl group (any -CH at any position in the alkyl group) 2 -CH 2 - is a group replaced by -O-CO-, an alkylcarbonyl group (any -CH at any position in the alkyl group) 2 - is a group replaced by -CO-, an alkylcarbonyloxy group (any -CH at any position in the alkyl group) 2 -CH 2 - is a group replaced by -CO-O-, an alkanedioxy group (any -CH at any position in the alkanedioxy group) 2 - is a group replaced by -O-, an alkanedioxycarbonyl group (any -CH at any position in the alkanedioxy group) 2 -CH 2 - is a group replaced by -O-CO-, an alkanediylcarbonyl group (any -CH at any position in the alkanediyl group) 2 - is a group replaced by -CO-, an alkanediylcarbonyloxy group (any -CH at any position in the alkanediyl group) 2 -CH 2 - is a group replaced by -CO-O-, an alkylthio group (any -CH at any position in the alkyl group) 2 - is a group replaced by -S-, an alkylsulfonyl group (any -CH at any position in the alkyl group) 2 - is replaced by -SO 2 - a group, a cycloalkoxy group, a cycloalkylalkoxy group, an alkoxycarbonyloxy group, an aromatic hydrocarbon group-carbonyl-oxy group, a group combining two or more of these groups, etc. may be mentioned. Examples of the alkoxy group include alkoxy groups having 1 to 17 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, an undecyloxy group, etc. The number of carbon atoms of the alkoxy group is preferably 1 to 11, more preferably 1 to 6, and still more preferably 1 to 4. An alkoxycarbonyl group, an alkylcarbonyl group, and an alkylcarbonyloxy group represent a group 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 17 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 18 carbon atoms, such as an acetyl group, a propionyl group, and a butyryl group. Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having 2 to 17 carbon atoms, such as an acetyloxy group, a propionyloxy group, and a butyryloxy group. Examples of the alkanedioxy group include alkanedioxy groups having 1 to 17 carbon atoms, such as a methyleneoxy group, an ethyleneoxy group, a propanedioloxy group, a butanedioloxy group, and a pentanedioloxy group. Examples of the alkanedioxycarbonyl group include alkanedioxycarbonyl groups having 2 to 17 carbon atoms, such as a methyleneoxycarbonyl group, an ethyleneoxycarbonyl group, a propanedioloxycarbonyl group, and a butanedioloxycarbonyl group. Examples of the alkanediylcarbonyl group include alkanediylcarbonyl groups having 2 to 18 carbon atoms, such as a methylenecarbonyl group, an ethylenecarbonyl group, a propanediylcarbonyl group, a butanediylcarbonyl group, and a pentanediylcarbonyl group. Examples of the alkanediylcarbonyloxy group include alkanediylcarbonyloxy groups having 2 to 17 carbon atoms, such as a methylenecarbonyloxy group, an ethylenecarbonyloxy group, a propanediylcarbonyloxy group, and a butanediylcarbonyloxy group. Examples of the alkylthio group include alkylthio groups having 1 to 17 carbon atoms, such as a methylthio group, an ethylthio group, and a propylthio group. The number of carbon atoms of the alkylthio group is preferably 1 to 11, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 17 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group and the like. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the cycloalkoxy group include cycloalkoxy groups having 3 to 17 carbon atoms, such as cyclohexyloxy group and the like. Examples of the cycloalkylalkoxy group include cycloalkylalkoxy groups having 4 to 17 carbon atoms, such as cyclohexylmethoxy group and the like. Examples of the alkoxycarbonyloxy group include alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as butoxycarbonyloxy group and the like. Examples of the aromatic hydrocarbon group-carbonyl oxy group include aromatic hydrocarbon group-carbonyl oxy groups having 7 to 17 carbon atoms, such as benzoyloxy group and the like. In particular, -CH 2 - contained in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO 2 - Examples of the resulting group include the groups shown below. The positions of -O- or -CO- in the groups shown below may be replaced by -S- or -SO 2 - respectively. The bonding site can be at any position. TIFF0007691875000012.tif47167

[0013] L 10 Examples of the substituents that the hydrocarbon group of may have include halogen atoms, cyano groups and the like. The hydroxy group, carboxy group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group are groups in which -CH 2 - contained in the hydrocarbon group is replaced by -O- or -CO-. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom and the like. L 10 The divalent hydrocarbon group having 1 to 36 carbon atoms of may have one substituent or a plurality of substituents.

[0014] L 10 is a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH contained in the alkanediyl group 2 - may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH contained in the alicyclic hydrocarbon group 2 - may be replaced by -O-, -S-, -SO 2 -, or -CO-), an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH contained in the alkanediyl group 2 - may be replaced by -O- or -CO-, and -CH contained in the alicyclic hydrocarbon group 2 - may be replaced by -O-, -S-, -SO 2 -, or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH contained in the alkanediyl group 2 - may be replaced by -O- or -CO-), and it is preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH contained in the alkanediyl group 2 - may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH contained in the alicyclic hydrocarbon group 2 - may be replaced by -O- or -CO-), a phenylene group which may have a substituent, a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH contained in the alkanediyl group 2 - may be replaced by -O- or -CO-, and -CH contained in the alicyclic hydrocarbon group 2 - may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and a phenylene group which may have a substituent (provided that -CH contained in the alkanediyl group 2- may be replaced by -O- or -CO-. It is more preferable that it is), and a single bond or an alkanediyl group having 1 to 4 carbon atoms (provided that -CH contained in the alkanediyl group 2 - may be replaced by -O- or -CO-. It is even more preferable that it is).

[0015] R 1 、R 2 and R 3 The bonding positions of 1 、X 2 and X 3 can be any of the ortho, meta, and para positions with respect to the bonding positions of 1 、X 2 and X 3 . Among them, it is preferable that it is bonded to the para position with respect to the bonding positions of

[0016] R 4 、R 5 、R 6 、R 7 、R 8 and R 9 Examples of the halogen atoms of R 4 、R 5 、R 6 、R 7 、R 8 and R 9 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. The alkyl fluoride group having 1 to 12 carbon atoms of R 4 、R 5 、R 6 、R 7 、R 8 and R9 Examples of the hydrocarbon group having 1 to 18 carbon atoms include chain hydrocarbon groups such as alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups 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, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 9, still more preferably 1 to 6, and even more preferably 1 to 4. The alicyclic hydrocarbon group may be monocyclic or polycyclic, and examples of the alicyclic hydrocarbon group include the groups represented below. The bonding site can be at any position. TIFF0007691875000013.tif44168Specifically, 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. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 16, still more preferably 3 to 12. Examples of the aromatic hydrocarbon group include 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 18, more preferably 6 to 14, still more preferably 6 to 10. Examples of the group formed by combination include a group combining an aromatic hydrocarbon group and a chain hydrocarbon group (e.g., aromatic hydrocarbon group - alkane diyl group - *, alkyl group - aromatic hydrocarbon group - *), a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (e.g., alicyclic hydrocarbon group - alkane diyl group - *, alkyl group - alicyclic hydrocarbon group - *), and a group combining an aromatic hydrocarbon group and an alicyclic hydrocarbon group (e.g., aromatic hydrocarbon group - alicyclic hydrocarbon group - *, alicyclic hydrocarbon group - aromatic hydrocarbon group - *). * represents a bonding site. Examples of the aromatic hydrocarbon group - alkane diyl 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, etc. Examples of the alicyclic hydrocarbon group - alkane diyl group - * include cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1-yl)-1-methylethyl, etc. 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, etc. Examples of the aromatic hydrocarbon group - alicyclic hydrocarbon group - * include phenylcyclohexyl group, etc. Examples of the alicyclic hydrocarbon group - aromatic hydrocarbon group - * include cyclohexylphenyl group, etc. In the combination, two or more alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined respectively. Further, -CH 2 - in the cyclic hydrocarbon group and the chain hydrocarbon group (alkane diyl group, alkyl group) may be replaced by -O-, -S-, -CO- or -SO 2 -. The combined group may have any group bonded to the benzene ring. -CH 2 - in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2- as the group replaced, a hydroxy group (-CH contained in a methyl group 2 - is a group replaced by -O-), a carboxy group (-CH contained in an ethyl group 2 -CH 2 - is a group replaced by -O-CO-), a thiol group (-CH contained in a methyl group 2 - is a group replaced by -S-), an alkoxy group (any position -CH contained in an alkyl group 2 - is a group replaced by -O-), an alkylthio group (any position -CH contained in an alkyl group 2 - is a group replaced by -S-), an alkoxycarbonyl group (any position -CH contained in an alkyl group 2 -CH 2 - is a group replaced by -O-CO-), an alkylsulfonyl group (any position -CH contained in an alkyl group 2 - is replaced by -SO 2 -), an alkylcarbonyl group (any position -CH contained in an alkyl group 2 - is a group replaced by -CO-), an alkylcarbonyloxy group (any position -CH contained in an alkyl group 2 -CH 2 - is a group replaced by -CO-O-), a cycloalkoxy group, a cycloalkylalkoxy group, an alkoxycarbonyloxy group, an aromatic hydrocarbon group-carbonyl-oxy group, a group formed by combining two or more of these groups, and the like can be mentioned. Examples of the alkoxy group include alkoxy groups having 1 to 17 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, an undecyloxy group, and the like. The number of carbon atoms of the alkoxy group is preferably 1 to 11, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkylthio group include alkylthio groups having 1 to 17 carbon atoms, such as methylthio group, ethylthio group, propylthio group, butylthio group and the like. The number of carbon atoms of the alkylthio group is preferably 1 to 11, more preferably 1 to 6, and still 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 17 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and the like. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 18 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 17 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 11, more preferably 2 to 6, and still more preferably 2 to 4. The number of carbon atoms of the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. The number of carbon atoms of the alkylcarbonyloxy group is preferably 2 to 11, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 17 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group and the like. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, and still more preferably 1 to 4. 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. In addition, -CH 2 - contained in the alicyclic hydrocarbon group may be replaced with -O-, -CO-, -S- or -SO 2 - to give groups such as those represented below. The positions of -O- or -CO- in the groups represented below may each be replaced with -S- or -SO 2 -. The bonding site can be at any position. TIFF0007691875000014.tif47167 -CH contained in the hydrocarbon group 2 - may be replaced with -O-, -CO-, -S- or -SO 2 -. When -CH is replaced, the total number of carbon atoms of the hydrocarbon group before replacement is taken as the total number of carbon atoms of the hydrocarbon group. Also, the number may be one or two or more. R 4 、R 5 、R 6 、R 7 、R 8 and R 9 The hydrocarbon group of may optionally have a substituent such as a halogen atom, a cyano group, or an alkyl group having 1 to 12 carbon atoms (wherein -CH 2 - contained in the alkyl group may be replaced with -O- or -CO-). 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. As a substituent, -CH contained in the alkyl group 2- When it is replaced by -O- or -CO-, the number of carbon atoms before replacement is defined as the total number of carbon atoms of the alkyl group. Examples of the replaced group include a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, and the like. Examples of the alkoxy group, the alkoxycarbonyl group, the alkylcarbonyl group, and the alkylcarbonyloxy group include the same groups as those described above. The hydrocarbon group may have one substituent or a plurality of substituents.

[0017] X 1 is preferably an oxygen atom. X 2 is preferably an oxygen atom. X 3 is preferably an oxygen atom. X 1 X 2 and X 3 The bonding positions of + may be any of the ortho, meta, and para positions with respect to the bonding position of S + . Among them, it is preferably bonded to the para or meta position with respect to the bonding position of S m1 is preferably 0, 1, or 2, more preferably 1 or 2, and even more preferably 1. m2 is preferably 0, 1, or 2, and more preferably 0 or 1. m3 is preferably 0 or 1, and more preferably 0. m4 is preferably 0, 1, 2, or 4, and more preferably 1 or 2. m5 is preferably 0, 1, or 2. When m4 and m5 are 1 or more, the bonding positions thereof may be any of the ortho, meta, and para positions. Among them, when m4 and m5 are both 2, it is preferably bonded to the para position with respect to each other. m6 is preferably 0 or 1, and more preferably 0. m7 is preferably 0, 1 or 2, more preferably 0. m8 is preferably 0 or 1. When m2 is 1, it is more preferably 0. When m2 is 0, it is more preferably 1. m9 is preferably 0 or 1. When m1 and m2 are both 1, it is more preferably 1. Among them, at least one of m8 and m9 is preferably an integer of 1 or more, and both m8 and m9 are preferably integers of 1 or more. In addition, when any one of m1 to m3 is 2 or more, or when any two of m1, m2 and m3 are 1 or more, the groups in the plurality of parentheses may be the same or different from each other. That is, X 1 ~X 3 When there are a plurality of each, R 1 ~R 3 When there are a plurality of each, R 4 ~R 6 When there are a plurality of each, these may all be the same or different from each other. R 4 、R 5 and R 6 are each independently a halogen atom, a C1-C4 fluoroalkyl group or a C1-C6 alkyl group (the -CH 2 - in the alkyl group may be replaced by -O- or -CO-). It is preferably a halogen atom, a C1-C4 fluoroalkyl group or a C1-C4 alkyl group (the -CH 2 - in the alkyl group may be replaced by -O- or -CO-). It is more preferably a fluorine atom, an iodine atom, a trifluoromethyl group or a C1-C4 alkyl group. R 7 、R 8 and R 9 are each independently a halogen atom, a C1-C4 fluoroalkyl group or a C1-C6 alkyl group (the -CH 2- may be replaced by -O- or -CO. It is preferably a halogen atom, an alkyl fluoride group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms (the -CH contained in the alkyl group 2 - may be replaced by -O- or -CO. It is more preferably a fluorine atom, an iodine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms (the -CH contained in the alkyl group 2 - may be replaced by -O- or -CO. It is even more preferably a fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, a t-butyl group, a hydroxy group, or a methoxy group. R 7 R 8 and R 9 The bonding positions of are not particularly limited. When m2 is 0, the bonding position of R 8 may be any of the ortho, meta, and para positions with respect to the bonding position of S + , and among them, it is more preferably bonded to the para position with respect to the bonding position of S + . When m3 is 0, the bonding position of R 9 may be any of the ortho, meta, and para positions with respect to the bonding position of S + , and among them, it is more preferably bonded to the para position with respect to the bonding position of S + . X 4 is preferably a single bond, -CH 2 -, -O-, -CO-, more preferably a single bond, -CH 2 -, and even more preferably a single bond.

[0018] Examples of the cation of salt (I) include cations represented by the following formulas (I-c-1) to (I-c-45). TIFF0007691875000015.tif231141

[0019] TIFF0007691875000016.tif225162

[0020] TIFF0007691875000017.tif238165

[0021] TIFF0007691875000018.tif141161

[0022] 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, alkynyl groups, and alicyclic hydrocarbon groups), aromatic hydrocarbon groups, and groups combining these. The -CH 2 - contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO-, or -SO 2 -. 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, 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, 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, etc. The -CH 2 - contained in the chain hydrocarbon group is replaced by -O-, -S-, -CO-, or -SO 2 - include a hydroxy group (a group in which -CH 2 - contained in the methyl group is replaced by -O-), a carboxy group (a group in which -CH 2 -CH 2 - contained in the ethyl group is replaced by -O-CO-), a thiol group (a group in which -CH 2 - contained in the methyl group is replaced by -S-), an alkoxy group (any -CH in the alkyl group2 - being a group replaced by -O-, an alkylthio group (any -CH at any position contained in the alkyl group) 2 - being a group replaced by -S-, an alkoxycarbonyl group (any -CH at any position contained in the alkyl group) 2 -CH 2 - being a group replaced by -O-CO-, an alkylcarbonyl group (any -CH at any position contained in the alkyl group) 2 - being a group replaced by -CO-, an alkylsulfonyl group (any -CH at any position contained in the alkyl group) 2 - being a group replaced by -SO 2 - a group replaced by -SO-, an alkylcarbonyloxy group (any -CH at any position contained in the alkyl group) 2 -CH 2 - being a group replaced by -CO-O-, an alkylthio group (any -CH at any position contained in the alkyl group) 2 - being a group replaced by -S-, etc. can be mentioned. As for the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, and alkylthio group, the same groups as described above can be mentioned. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 17 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, etc. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, and still more preferably 1 to 4. In addition, the replacement in the alkenyl group and alkynyl group may be any one containing a carbon-carbon double bond or a carbon-carbon triple bond at any position in the examples of the replacement in the above-mentioned alkyl group. The alicyclic hydrocarbon group may be any of monocyclic, polycyclic, and spiro ring, and may be either 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, etc., and polycyclic cycloalkyl groups such as norbornyl group, adamantyl group, etc. The alicyclic hydrocarbon group and -CH contained in the alicyclic hydrocarbon group2 - is replaced by -O-, -S-, -CO- or -SO 2 As the group replaced by -, specifically, the following groups and the like can be mentioned. The bonding site can be at any position. TIFF0007691875000019.tif116159 an alicyclic hydrocarbon group or -CH contained in an alicyclic hydrocarbon group 2 - is replaced by -O-, -S-, -CO- or -SO 2 As the group replaced by -, the groups represented by formulas (y1) to (y71) are preferable, the groups represented by any of formula (y1) to formula (y20), formula (y26), formula (y27), formula (y30), formula (y31), formula (y39) to formula (y71) are more preferable, and the 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), formula (y49) to formula (y58), formula (y62) to formula (y71) are further preferable. 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.

[0023] 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, alkanetetrayl group, cycloalkanediyl group, cycloalkanetriyl group, cycloalkanetetrayl group, etc.) in the above-mentioned groups may be included.

[0024] The combined group means a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (the -CH contained in the chain hydrocarbon group and the alicyclic hydrocarbon group) 2- may be replaced by -O-, -S-, -CO- or -SO 2 (which may be replaced by -O-, -S-, -CO- or -SO) a group combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group (wherein -CH 2 - may be replaced by -O-, -S-, -CO- or -SO 2 (which may be replaced by -O-, -S-, -CO- or -SO), and a group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (wherein -CH 2 - may be replaced by -O-, -S-, -CO- or -SO 2 (which may be replaced by -O-, -S-, -CO- or -SO). In the combination, the alicyclic hydrocarbon group, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may each be combined with two or more kinds thereof. Specifically, as the combined group, an alicyclic hydrocarbon group - aliphatic hydrocarbon group - *, such as an adamantylmethylene group, a cyclohexylmethylene group, etc. (alicyclic hydrocarbon group) 2 - aliphatic hydrocarbon group - * (wherein -CH 2 - may be replaced by -O-, -S-, -CO- or -SO 2 (which may be replaced by -O-, -S-, -CO- or -SO), an aliphatic hydrocarbon group - alicyclic hydrocarbon group - *, such as a methyladamantyl group, a dimethyladamantyl group, etc. (aliphatic hydrocarbon group) 2 - alicyclic hydrocarbon group - * (wherein -CH 2 - may be replaced by -O-, -S-, -CO- or -SO 2 (which may be replaced by -O-, -S-, -CO- or -SO), an aliphatic hydrocarbon group - aromatic hydrocarbon group - *, such as a tolyl group, a xylyl group, etc. (wherein -CH 2 - may be replaced by -O-, -S-, -CO- or -SO 2 (which may be replaced by -O-, -S-, -CO- or -SO), an aliphatic hydrocarbon group - alicyclic hydrocarbon group - aliphatic hydrocarbon group - *, such as a methylcyclohexylmethylene group, etc. (aliphatic hydrocarbon group) 2 - alicyclic hydrocarbon group - aliphatic hydrocarbon group - * (aliphatic hydrocarbon group - alicyclic hydrocarbon group) 2-chain hydrocarbon group-*(The -CH contained in the chain hydrocarbon group and the alicyclic hydrocarbon group 2 -may be replaced by -O-, -S-, -CO- or -SO 2 -), aromatic hydrocarbon group such as benzyl group-chain hydrocarbon group-*(The -CH contained in the chain hydrocarbon group 2 -may be replaced by -O-, -S-, -CO- or -SO 2 -), chain hydrocarbon group such as tolylmethyl group-aromatic hydrocarbon group-chain hydrocarbon group-*(The -CH contained in the chain hydrocarbon group 2 -may be replaced by -O-, -S-, -CO- or -SO 2 -), chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-*, (chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group) 2 -alicyclic hydrocarbon group-*, (chain hydrocarbon group-alicyclic hydrocarbon group) 2 -chain hydrocarbon group-alicyclic hydrocarbon group-*, (chain hydrocarbon group) 2 -alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-*(The -CH contained in the chain hydrocarbon group and the alicyclic hydrocarbon group 2 -may be replaced by -O-, -S-, -CO- or -SO 2 -), alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-*, (alicyclic hydrocarbon group) 2 -chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-*, (alicyclic hydrocarbon group-chain hydrocarbon group) 2 -alicyclic hydrocarbon group-chain hydrocarbon group-*, (alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group) 2 -chain hydrocarbon group-*(The -CH contained in the chain hydrocarbon group and the alicyclic hydrocarbon group 2 -may be replaced by -O-, -S-, -CO- or -SO 2 -), Chain hydrocarbon group - alicyclic hydrocarbon group - chain hydrocarbon group - alicyclic hydrocarbon group - chain hydrocarbon group - *, (chain hydrocarbon group) 2 - alicyclic hydrocarbon group - chain hydrocarbon group - alicyclic hydrocarbon group - chain hydrocarbon group - *, (chain hydrocarbon group - alicyclic hydrocarbon group) 2 - chain hydrocarbon group - alicyclic hydrocarbon group - chain hydrocarbon group - *, (chain hydrocarbon group - alicyclic hydrocarbon group - chain hydrocarbon group) 2 - alicyclic hydrocarbon group - chain hydrocarbon group - *, (chain hydrocarbon group - alicyclic hydrocarbon group - chain hydrocarbon group - alicyclic hydrocarbon group) 2 - chain hydrocarbon group - *, (the -CH contained in the chain hydrocarbon group and the alicyclic hydrocarbon group) 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -). etc. Here, * represents the bonding position with the carbon atom of the carbonyl group.

[0025] X 0 In the hydrocarbon group represented by, the -CH 2 - is replaced by -O-, -S-, -CO- or -SO 2 -, the total number of carbon atoms before replacement is taken as the total number of carbon atoms of the hydrocarbon group. Also, when a substituent is bonded to the hydrocarbon group represented by X 0 , the total number of carbon atoms before substitution is taken as the total number of carbon atoms of the hydrocarbon group. X 0 The hydrocarbon group represented by may 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 formed by combining these. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group, etc. Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group, 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 groups 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 methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, etc. Examples of the alkylcarbonyl group having 2 to 13 carbon atoms include acetyl group, propionyl group, butyryl group, etc. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include acetyloxy group, propionyloxy group, butyryloxy group, etc. 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 the bonding position with X Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include aryl groups such as phenyl group and naphthyl group. Examples of the combined groups include a group combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms, a group combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, a group combining an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, etc. Examples of the group 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 hydroxymethyl group and 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.

[0026] 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 -CH 2 - in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -), or an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent, more preferably an alicyclic hydrocarbon group which may have a hydroxy group or a fluorine atom (wherein -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -), a group formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group (wherein -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -, and -CH 2 - 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 perfluoroalkyl group having 1 to 4 carbon atoms, a group represented by formula (aa) or a group represented by formula (bb), even more preferably a *-alicyclic hydrocarbon group (wherein -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -, and the alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom. * is -COO -represents the bonding position with the carbon atom of)., *-alicyclic hydrocarbon group - chain hydrocarbon group (the -CH contained in the alicyclic hydrocarbon group 2 - may be replaced by -O-, -S-, -CO- or -SO 2 - and the -CH contained in the chain hydrocarbon group may also 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. * is -COO 2 represents the bonding position with the carbon atom of).), *-chain hydrocarbon group - alicyclic hydrocarbon group (the -CH contained in the chain hydrocarbon group - - may be replaced by -O- or -CO-, and the -CH contained in the alicyclic hydrocarbon group 2 - may be replaced by -O-, -S-, -CO- or -SO 2 - and the chain hydrocarbon group and the alicyclic hydrocarbon group may have a fluorine atom or a hydroxy group. * is -COO 2 represents the bonding position with 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), - more preferably, *-polycyclic alicyclic hydrocarbon group (the -CH contained in the polycyclic alicyclic hydrocarbon group - may be replaced by -O-, -S-, -CO- or -SO 2 - and the polycyclic alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom. * is -COO 2 represents the bonding position with the carbon atom of).), *-polycyclic alicyclic hydrocarbon group - chain hydrocarbon group (the -CH contained in the polycyclic alicyclic hydrocarbon group - - may be replaced by -O-, -S-, -CO- or -SO 2 - and the -CH 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. * is -COO 2 represents the bonding position with the carbon atom of).), *-chain hydrocarbon group - polycyclic alicyclic hydrocarbon group (the -CH contained in the chain hydrocarbon group 2 - 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. * is -COO - represents the bonding position with the carbon atom of).), *-chain hydrocarbon group - polycyclic alicyclic hydrocarbon group (the -CH contained in the chain hydrocarbon group2 - may be replaced by -O- or -CO-, and -CH- contained in the polycyclic alicyclic hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 - may be replaced, and the chain hydrocarbon group and the polycyclic alicyclic hydrocarbon group may have a fluorine atom or a hydroxy group. * is -COO - represents the bonding position to the carbon atom of). It is an aromatic hydrocarbon group which may have a fluorine atom or a hydroxy group, a group represented by formula (aa) or a group represented by formula (bb), Particularly preferably, it is an adamantanone group, a hydroxyadamantyl group, a group combining an adamantyl group and an alkyl group (-CH- contained in the alkyl group 2 - may be replaced by -O- or -CO-). It is a group represented by formula (Y30F) or a phenyl group having a hydroxy group. In the above groups, 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. The number of carbon atoms of 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 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. TIFF0007691875000021.tif26125 [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 -CH- contained in the hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 - may be replaced. X 2arepresents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, and -CH contained in the hydrocarbon group 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -. * 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 -CH contained in the alkanediyl group 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -. R A represents a hydrocarbon group having 1 to 36 carbon atoms which may have a substituent, and -CH contained in the hydrocarbon group 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -. * represents the bonding position with the carbon atom of -COO - .]

[0027] X a and X b are preferably the same atom, and more preferably both are oxygen atoms.

[0028] X 1a and X 2a Examples of the hydrocarbon group represented by 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 a substituent. Also, -CH contained in these hydrocarbon groups 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -. Here, the number of carbon atoms of the hydrocarbon group means the number of carbon atoms of the hydrocarbon group without a substituent and without replacement.

[0029] X 1a Examples of the aliphatic hydrocarbon group of X include chain hydrocarbon groups such as alkanetriyl groups, alicyclic hydrocarbon groups, or groups combining these. Specific examples of the alkanetriyl group include methine group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decanetriyl group, undecanetriyl group, dodecanetriyl group, and the like.

[0030] The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cyclooctanetriyl group, and the like. Examples of the polycyclic alicyclic hydrocarbon group include norbornanetriyl group, adamantantriyl group, and the like. Examples of the aromatic hydrocarbon group include benzenetriyl group, naphthalenetriyl group, anthracenetriyl group, and the like. In the case of the combined group, groups with different valences in the above-mentioned groups (alkyl group, alkanediyl group, alkanetetrayl group, cycloalkyl group, cycloalkanediyl group, cycloalkanetetrayl group, etc.) may be included.

[0031] 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 hydroxy group, halogen atom, cyano group, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, alkoxycarbonyl group having 2 to 13 carbon atoms, alkylcarbonyl group having 2 to 13 carbon atoms, alkylcarbonyloxy group having 2 to 13 carbon atoms, alicyclic hydrocarbon group having 3 to 12 carbon atoms, 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 a group formed by combining these are the same groups as described above.

[0032] 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 or a group represented by formula (w1-1) to formula (w1-11), and even 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). TIFF0007691875000022.tif53144[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 formed by combining these. * represents a bonding position.]

[0033] X 2a The number of carbon atoms of the hydrocarbon group represented by [X] is preferably 2 to 48, more preferably 4 to 48, even more preferably 6 to 44, still more preferably 8 to 40, and even still more preferably 10 to 38.

[0034] X 2aExamples of the substituent that the hydrocarbon group in [compound name] may have 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 formed by combining these groups. Examples of the halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and a group formed by combining these groups are the same as those described above. X 2a The hydrocarbon group having 1 to 48 carbon atoms represented by [formula] may have one substituent or a plurality of substituents.

[0035] X 2a Examples of the hydrocarbon group in [compound name] include a linear or branched chain hydrocarbon group (e.g., an alkanediyl group), a monocyclic or polycyclic alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and a combination of two or more of these groups is also possible. 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; 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, a 2-methylbutane-1,4-diyl group; Monocyclic alicyclic hydrocarbon groups that are monocyclic cycloalkanediyl groups such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cyclooctane-1,5-diyl group; A polycyclic alicyclic hydrocarbon group which is a polycyclic cycloalkanediyl group such as a norbornane-1,4-diyl group, a norbornane-2,5-diyl group, an adamantane-1,5-diyl group, an adamantane-2,6-diyl group; Examples thereof include aromatic hydrocarbon groups such as a phenylene group, a naphthylene group, a biphenylene group, an anthrylene group, a phenanthrylene group, and a binaphthylene group. In the case of a combined group, groups having different valences in the above-mentioned groups (alkyl group, alkanetriyl group, alkanetetrayl group, cycloalkyl group, cycloalkanetriyl group, cycloalkanetetrayl group, etc.) may be included. Examples of the combined group include a group combining a chain hydrocarbon group and an alicyclic hydrocarbon group, a group combining a chain hydrocarbon group and an aromatic hydrocarbon group, a group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group, etc. Specifically, a group in which one or more alicyclic hydrocarbon groups are bonded to a chain hydrocarbon group (for example, -chain hydrocarbon group-alicyclic hydrocarbon group, -chain hydrocarbon group-(alicyclic hydrocarbon group) 2 etc.), a group in which one or more chain hydrocarbon groups are bonded to an alicyclic hydrocarbon group (for example, -alicyclic hydrocarbon group-chain hydrocarbon group, -alicyclic hydrocarbon group-(chain hydrocarbon group) 2 etc.), a group in which one or more alicyclic hydrocarbon groups and a chain hydrocarbon group are bonded to a chain hydrocarbon group (for example, -chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group, -chain hydrocarbon group-(alicyclic hydrocarbon group-chain hydrocarbon group) 2 etc.) etc. are included.

[0036] X 2a As the hydrocarbon group in, an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the -CH 2 - contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -, and the alicyclic hydrocarbon group may have a substituent.), a chain hydrocarbon group having 2 to 18 carbon atoms (the -CH 2 - contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the chain hydrocarbon group may have a substituent.), or, A chain hydrocarbon group having 1 to 12 carbon atoms (wherein -CH 2 - in the chain hydrocarbon group may be replaced by -O- or -CO-.) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (wherein -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -.) A group formed by combining them (the group may have a substituent) is preferable, A chain hydrocarbon group having 4 to 18 carbon atoms (wherein -CH 2 - in the chain hydrocarbon group may be replaced by -O- or -CO-, and the chain hydrocarbon group may have a substituent.), or A chain hydrocarbon group having 1 to 12 carbon atoms (wherein -CH 2 - in the chain hydrocarbon group may be replaced by -O- or -CO-.) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms (wherein -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -.) A group formed by combining them (the group may have a substituent) is more preferable, A chain hydrocarbon group having 6 to 14 carbon atoms (wherein -CH 2 - in the chain hydrocarbon group may be replaced by -O- or -CO-, and the chain hydrocarbon group may have a substituent.), or A chain hydrocarbon group having 1 to 12 carbon atoms (wherein -CH 2 - in the chain hydrocarbon group may be replaced by -O- or -CO-.) and an alicyclic hydrocarbon group having 5 to 14 carbon atoms (wherein -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -.) A group formed by combining them (the group may have a substituent) is even more preferable.

[0037] Specifically, as the hydrocarbon group in X 2a is, An alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (wherein -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -), An alkanediyl group having 2 to 18 carbon atoms which may have a substituent (wherein -CH 2 - in the alkanediyl group may be replaced by -O- or -CO-), An alkanediyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH 2 - in the alkanediyl 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 -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -), or An alkanediyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH 2 - in the alkanediyl 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 -CH 2 - in the alkyl group may be replaced by -O- or -CO-), and it is preferably a group composed of An alkanediyl group having 4 to 18 carbon atoms which may have a substituent (wherein -CH 2 - in the alkanediyl group may be replaced by -O- or -CO-), An alkanediyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH 2 - in the alkanediyl group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms which may have a substituent (wherein -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -), or An alkanediyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH 2 - contained in the alkanediyl group may be replaced by -O- or -CO-), an alicyclic 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 -CH 2 - contained in the alkyl group may be replaced by -O- or -CO-). It is more preferably a group composed of An alkanediyl group having 6 to 14 carbon atoms which may have a substituent (wherein -CH 2 - contained in the alkanediyl group may be replaced by -O- or -CO-), An alkanediyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH 2 - contained in the alkanediyl group may be replaced by -O- or -CO-), and an adamantanediyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH 2 - contained in the adamantanediyl group may be replaced by -O- or -CO-), or An alkanediyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH 2 - contained in the alkanediyl group may be replaced by -O- or -CO-), an adamantanediyl group having 1 to 12 carbon atoms which may have a substituent, and an alkyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH 2 - contained in the alkyl group may be replaced by -O- or -CO-). It is even more preferably a group composed of

[0038] 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). TIFF0007691875000023.tif33158 [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, and -CH 2 - contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -, 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 a combination of 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.

[0039] Among them, R 1x , R 2x , R 3x , R 4x , R 5x and R 6x are, as an alkyl group having 1 to 6 carbon atoms (where -CH 2 - 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 (where -CH 2 - contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -, and the alicyclic hydrocarbon group may have a substituent.), or an alkyl group having 1 to 6 carbon atoms (where -CH 2 - contained in the alkyl group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 5 to 12 carbon atoms (where -CH 2 - contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -), and a group formed by combining them (the group may have a substituent) is preferred, and a methoxy group, an adamantyl group (where -CH 2- may be replaced by -O- or -CO-, and the adamantyl group may have a substituent. ) or an alkyl group having 1 to 6 carbon atoms (the -CH contained in the alkyl group 2 - may be replaced by -O- or -CO-. ) and a group combined with an adamantyl group (the group may have a substituent). It is more preferable that it is such a group.

[0040] In formula (bb), L A and L B Examples of the alkanediyl group having 1 to 6 carbon atoms in 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; 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 that 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. -CH contained in the alkanediyl group 2 - When it is replaced by -O- or -CO-, the total number of carbon atoms before replacement is taken as the total number of carbon atoms of the alkanediyl group. The alkanediyl group is a hydroxy group (a group in which -CH contained in the methyl group 2 - is replaced by -O-), a carboxy group (a group in which -CH contained in the ethyl group 2 -CH 2 - is replaced by -O-CO-), an alkoxy group (a group in which -CH at any position contained in the alkyl group 2 - is replaced by -O-), an alkoxycarbonyl group (a group in which -CH at any position contained in the alkyl group 2 -CH 2- is a group replaced by -O-CO-), an alkylcarbonyl group (any -CH at any position contained in the alkyl group) 2 - is a group replaced by -CO-), an alkylcarbonyloxy group (any -CH at any position contained in the alkyl group) 2 -CH 2 - is a group replaced by -CO-O-), an alkanediyl-oxy group (any -CH at any position contained in the alkanediyl group) 2 - is a group replaced by -O-), an alkanediyl-oxycarbonyl group (any -CH at any position contained in the alkanediyl group) 2 -CH 2 - is a group replaced by -O-CO-), an alkanediyl-carbonyl group (any -CH at any position contained in the alkanediyl group) 2 - is a group replaced by -CO-), an alkanediyl-carbonyl-oxy group (any -CH at any position contained in the alkanediyl group) 2 -CH 2 - may have a group replaced by -CO-O-). Examples of the alkanediyl-oxy group include a methylene-oxy group, an ethylene-oxy group, a propane-diyl-oxy group, a butane-diyl-oxy group, a pentane-diyl-oxy group, and the like. Examples of the alkanediyl-oxycarbonyl group include a methylene-oxycarbonyl group, an ethylene-oxycarbonyl group, a propane-diyl-oxycarbonyl group, a butane-diyl-oxycarbonyl group, and the like. Examples of the alkanediyl-carbonyl group include a methylene-carbonyl group, an ethylene-carbonyl group, a propane-diyl-carbonyl group, a butane-diyl-carbonyl group, a pentane-diyl-carbonyl group, and the like. Examples of the alkanediyl-carbonyl-oxy group include a methylene-carbonyl-oxy group, an ethylene-carbonyl-oxy group, a propane-diyl-carbonyl-oxy group, a butane-diyl-carbonyl-oxy group, and the like.

[0041] L Ais 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 (the -CH contained in the alkanediyl group 2 - may be replaced by -O- or -CO-), and more preferably a single bond, a methylene group or an ethylene group.

[0042] R A Examples of the hydrocarbon group in include aliphatic hydrocarbon groups (chain hydrocarbon groups such as alkyl groups, alkenyl groups, alkynyl groups and alicyclic hydrocarbon groups), aromatic hydrocarbon groups and groups 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 and the like. 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. -CH contained in the chain hydrocarbon group 2 - may be -O-, -S-, -CO- or -SO 2Examples of the group replaced by - include a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkylthio group, an alkylsulfonyl group, and the like. Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alkylsulfonyl group, and alkylthio group include 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 alkylsulfonyl group having 1 to 17 carbon atoms, and an alkylthio group having 1 to 17 carbon atoms, and groups similar to the above-described groups.

[0043] The alicyclic hydrocarbon group may be monocyclic, polycyclic, or spiro, and may be saturated or unsaturated. Examples of the monocyclic alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, and a cyclododecyl group. Examples of the polycyclic alicyclic hydrocarbon group include polycyclic cycloalkyl groups such as a decahydronaphthyl group, an adamantyl group, and a norbornyl group. The alicyclic hydrocarbon group and -CH contained in the alicyclic hydrocarbon group 2 - is replaced by -O-, -S-, -CO-, or -SO 2 Specific examples of the group replaced include the groups represented by the above formulas (y1) to (y71) and the like. 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 a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, and a binaphthyl group. 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.

[0044] In the case of a combined group, groups with different valences (such as alkane diyl groups, alkane triyl groups, cycloalkane diyl groups, cycloalkane triyl groups, 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 - alkane diyl group - *, alkyl group - aromatic hydrocarbon group - *), a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (for example, alicyclic hydrocarbon group - alkane diyl 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 - alkane diyl 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, etc. Examples of the alicyclic hydrocarbon group - alkane diyl group - * include cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1-yl)-1-methylethyl, etc. 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, etc. Examples of the aromatic hydrocarbon group - alicyclic hydrocarbon group - * include phenyladamantyl group, etc. Examples of the alicyclic hydrocarbon group - aromatic hydrocarbon group - * include adamantylphenyl group, etc. In the combination, the alicyclic hydrocarbon group, aromatic hydrocarbon group, and chain hydrocarbon group may each be combined with two or more kinds. Also, any group may be bonded to L B It may be bonded.

[0045] -CH contained in the hydrocarbon group 2 - is replaced by -O-, -S-, -CO- or -SO 2 - In addition to the groups described above, examples of the group replaced include a cycloalkoxy group, a cycloalkylalkoxy group, an alkoxycarbonyloxy group, an aromatic hydrocarbon group-carbonyl oxy group, and a group obtained by combining 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. -CH contained in the hydrocarbon group 2 - is replaced by -O-, -S-, -SO 2 - or -CO-, the total carbon number of the hydrocarbon group before replacement is taken as the total carbon number of the hydrocarbon group. Also, the number may be one or two or more.

[0046] R A Examples of the substituent that the hydrocarbon group of may have include a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms (the -CH 2 - contained in the alkyl group may be replaced by -O-, -S-, -CO- or -SO 2 -). 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. -CH contained in the alkyl group 2 - is replaced by -O- or -CO-, and examples of the group include a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, and the like. Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, and 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. For example, the same groups as those described above can be mentioned. R A The hydrocarbon group in

[0047] R A The hydrocarbon group in may have one substituent or a plurality of substituents. 2 - in the alkyl group may be replaced by -O-, -S-, -CO- or -SO 2 - (provided that -CH 2 - in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 - (provided that -CH 2 - in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 - (provided that -CH

[0048] Examples of the cyclic hydrocarbon group include a cyclic hydrocarbon group such as a monocyclic or polycyclic alicyclic hydrocarbon group having 3 to 18 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group 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 of the groups may be bonded to L B

[0049] ​A 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 -CH contained in the alicyclic hydrocarbon group 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -), 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 (the -CH contained in the alicyclic hydrocarbon group 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -), or 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 is preferable, 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 (the -CH contained in the alicyclic hydrocarbon group 2 - may be replaced by -O- or -CO-) is more preferable. 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. TIFF0007691875000024.tif1687

[0050] Examples of the carboxylate anion in the carboxylate represented by the formula (I) include the carboxylate anions described below. TIFF0007691875000025.tif211162

[0051] TIFF0007691875000026.tif218162

[0052] TIFF0007691875000027.tif252158

[0053] TIFF0007691875000028.tif67157

[0054] Specific examples of the carboxylate (I) include salts formed 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). TIFF0007691875000029.tif4961 [Table 1] JPEG0007691875000031.jpg197156

[0055] Among them, as the carboxylate (I), a salt 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) and a cation represented by any one of the formulas (I-c-1) to (I-c-45) is preferable. Specifically, carboxylates (I-1) to (I-5), carboxylates (I-10) to (I-21), carboxylates (I-57) to (I-66), carboxylates (I-96) to (I-100), carboxylates (I-105) to (I-116), carboxylates (I-152) to (I-161), carboxylates (I-191) to (I-195), carboxylates (I-200) to (I-211), carboxylates (I-247) to (I-256), carboxylates (I-286) to (I-290), carboxylates (I-295) to (I-306), carboxylates (I-342) to (I-351), carboxylates (I-381) to (I-385), carboxylates (I-390) to (I-401), carboxylates (I-437) to (I-446), carboxylates (I-476) to (I-480), carboxylates (I-485) to (I-496), carboxylates (I-532) to (I-541), carboxylates (I-571) to (I-575), carboxylates (I-580) to (I-591), carboxylates (I-627) to (I-636), carboxylates (I-666) to (I-670), carboxylates (I-675) to (I-686), carboxylates (I-722) to (I-731), carboxylates (I-761) to (I-765), carboxylates (I-770) to (I-781), carboxylates (I-817) to (I-826), carboxylates (I-856) to (I-860), carboxylates (I-865) to (I-876), carboxylates (I-912) to (I-921).Carboxylates (I-951) to (I-955), carboxylates (I-960) to (I-971), carboxylates (I-1007) to (I-1016), carboxylates (I-1046) to (I-1050), carboxylates (I-1055) to (I-1066), carboxylates (I-1102) to (I-1111), carboxylates (I-1141) to (I-1145), carboxylates (I-1150) to (I-1161), carboxylates (I-1197) to (I-1206), carboxylates (I-1236) to (I-1240), carboxylates (I-1245) to (I-1256), carboxylates (I-1292) to (I-1301), carboxylates (I-1331) to (I-1335), carboxylates (I-1340) to (I-1351), carboxylates (I-1387) to (I-1396), carboxylates (I-1426) to (I-1430), carboxylates (I-1435) to (I-1446), carboxylates (I-1482) to (I-1491), carboxylates (I-1521) to (I-1525), carboxylates (I-1530) to (I-1541), carboxylates (I-1577) to (I-1586), carboxylates (I-1616) to (I-1620), carboxylates (I-1625) to (I-1636), carboxylates (I-1672) to (I-1681), carboxylates (I-1711) to (I-1715), carboxylates (I-1720) to (I-1731), carboxylates (I-1767) to (I-1776), carboxylates (I-1806) to (I-1810), carboxylates (I-1815) to (I-1826), carboxylates (I-1862) to (I-1871), carboxylates (I-1901) to (I-1905), carboxylates (I-1910) to (I-1921), carboxylates (I-1957) to (I-1966)Carboxylates (I-1996) to Carboxylates (I-2000), Carboxylates (I-2005) to Carboxylates (I-2016), Carboxylates (I-2052) to Carboxylates (I-2061), Carboxylates (I-2091) to Carboxylates (I-2095), Carboxylates (I-2100) to Carboxylates (I-2111), Carboxylates (I-2147) to Carboxylates (I-2156), Carboxylates (I-2186) to Carboxylates (I-2190), Carboxylates (I-2195) to Carboxylates (I-2206), Carboxylates (I-2242) to Carboxylates (I-2251), Carboxylates (I-2281) to Carboxylates (I-2285), Carboxylates (I-2290) to Carboxylates (I-2301), Carboxylates (I-2337) to Carboxylates (I-2346), Carboxylates (I-2376) to Carboxylates (I-2380), Carboxylates (I-2385) to Carboxylates (I-2396), Carboxylates (I-2432) to Carboxylates (I-2441), Carboxylates (I-2471) to Carboxylates (I-2475), Carboxylates (I-2480) to Carboxylates (I-2491), Carboxylates (I-2527) to Carboxylates (I-2536), Carboxylates (I-2566) to Carboxylates (I-2570), Carboxylates (I-2575) to Carboxylates (I-2586), Carboxylates (I-2622) to Carboxylates (I-2631), Carboxylates (I-2661) to Carboxylates (I-2665), Carboxylates (I-2670) to Carboxylates (I-2681), Carboxylates (I-2717) to Carboxylates (I-2726), Carboxylates (I-2756) to Carboxylates (I-2760), Carboxylates (I-2765) to Carboxylates (I-2776), Carboxylates (I-2812) to Carboxylates (I-2821), Carboxylates (I-2851) to Carboxylates (I-2855), Carboxylates (I-2860) to Carboxylates (I-2871), Carboxylates (I-2907) to Carboxylates (I-2916), Carboxylates (I-2946) to Carboxylates (I-2950), Carboxylates (I-2955) to Carboxylates (I-2966), Carboxylates (I-3002) to Carboxylates (I-3011)Carboxylates (I-3041) to Carboxylates (I-3045), Carboxylates (I-3050) to Carboxylates (I-3061), Carboxylates (I-3097) to Carboxylates (I-3106), Carboxylates (I-3136) to Carboxylates (I-3140), Carboxylates (I-3145) to Carboxylates (I-3156), Carboxylates (I-3192) to Carboxylates (I-3201), Carboxylates (I-3231) to Carboxylates (I-3235), Carboxylates (I-3240) to Carboxylates (I-3251), Carboxylates (I-3287) to Carboxylates (I-3296), Carboxylates (I-3326) to Carboxylates (I-3330), Carboxylates (I-3335) to Carboxylates (I-3346), Carboxylates (I-3382) to Carboxylates (I-3391), Carboxylates (I-3421) to Carboxylates (I-3425), Carboxylates (I-3430) to Carboxylates (I-3441), Carboxylates (I-3477) to Carboxylates (I-3486), Carboxylates (I-3516) to Carboxylates (I-3520), Carboxylates (I-3525) to Carboxylates (I-3536), Carboxylates (I-3572) to Carboxylates (I-3581), Carboxylates (I-3611) to Carboxylates (I-3615), Carboxylates (I-3620) to Carboxylates (I-3631), Carboxylates (I-3667) to Carboxylates (I-3676), Carboxylates (I-3706) to Carboxylates (I-3710), Carboxylates (I-3715) to Carboxylates (I-3726), Carboxylates (I-3762) to Carboxylates (I-3771), Carboxylates (I-3801) to Carboxylates (I-3805), Carboxylates (I-3810) to Carboxylates (I-3821), Carboxylates (I-3857) to Carboxylates (I-3866), Carboxylates (I-3896) to Carboxylates (I-3900), Carboxylates (I-3905) to Carboxylates (I-3916), Carboxylates (I-3952) to Carboxylates (I-3961), Carboxylates (I-3991) to Carboxylates (I-3995), Carboxylates (I-4000) to Carboxylates (I-4011), Carboxylates (I-4047) to Carboxylates (I-4056)Carboxylates (I-4086) to carboxylates (I-4090), carboxylates (I-4095) to carboxylates (I-4106), carboxylates (I-4142) to carboxylates (I-4151), carboxylates (I-4181) to carboxylates (I-4185), carboxylates (I-4190) to carboxylates (I-4201), carboxylates (I-4237) to carboxylates (I-4246) are preferred.

[0056] <Method for producing salt (I)> Salt (I) can be produced by reacting a salt represented by formula (I-a) with a salt represented by formula (I-b) in a solvent. TIFF0007691875000032.tif83159[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 together 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.

[0057] 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 include salts represented below. TIFF0007691875000033.tif99160

[0058] TIFF0007691875000034.tif31153

[0059] 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), the compound represented by formula (I-d2), and the compound represented by formula (I-d3) in a solvent in the presence of a catalyst. TIFF0007691875000035.tif78158[In the formula, all the symbols have the same meanings as described above.] Examples of the catalyst include carbonyldiimidazole and potassium hydroxide. Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, and water. The reaction temperature is usually from 15°C to 80°C, and the reaction time is usually from 0.5 to 24 hours.

[0060] Examples of the compound represented by formula (I-d1), the compound represented by formula (I-d2), and the compound represented by formula (I-d3) include the compounds represented below, etc. They can be easily obtained from the market and can also be easily produced by known production methods. TIFF0007691875000036.tif67154

[0061] The salt represented by formula (I-c) can be produced by reacting the salt represented by formula (I-e), the compound represented by formula (I-f1), the compound represented by formula (I-f2), and the compound represented by formula (I-f3) in a solvent in the presence of a catalyst. TIFF0007691875000037.tif79157[In the formula, all the symbols have the same meanings as described above.] Examples of the catalyst include potassium carbonate and sodium hydride. Examples of the solvent include chloroform, monochlorobenzene, acetonitrile, and water. The reaction temperature is usually from 15°C to 100°C, and the reaction time is usually from 0.5 to 24 hours.

[0062] 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. TIFF0007691875000038.tif62158

[0063] Examples of the compound represented by formula (I-f1), the compound represented by formula (I-f2), and the compound represented by formula (I-f3) include compounds represented by the following, and they can be easily obtained from the market. TIFF0007691875000039.tif20105

[0064] The salt represented by formula (I-c) can also be produced by reacting the salt represented by formula (I-e), the compound represented by formula (I-f4), the compound represented by formula (I-f5), and the compound represented by formula (I-f6) in a solvent in the presence of potassium carbonate, followed by acid treatment. TIFF0007691875000040.tif133153[In the formula, all symbols have the same meanings as described above. R ac represents an acid-labile group.] Examples of the solvent include chloroform, monochlorobenzene, acetonitrile, water, and the like. The reaction temperature is usually 15°C to 100°C, and the reaction time is usually 0.5 to 24 hours. Examples of the acid include p-toluenesulfonic acid, hydrochloric acid, and the like.

[0065] Examples of the compound represented by formula (I-f4), the compound represented by formula (I-f5), and the compound represented by formula (I-f6) include compounds represented by the following, and they can be easily obtained from the market. TIFF0007691875000041.tif78155

[0066] 〔Carboxylic acid generator〕 The carboxylic acid generator of the present invention is an acid generator containing a carboxylate (I). The carboxylate (I) of the present invention can act as an acid generator in a resist composition. When using the carboxylate (I) as an acid generator in a resist composition, the acid generator may contain only one type or two or more types of carboxylates (I). In addition, as will be described later, the acid generator of the present invention may further contain an acid generator known in the resist field other than the carboxylate (I) (hereinafter sometimes referred to as "acid generator (B)") and / or a carboxylic acid generator known in the resist field other than the 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 content of the carboxylate (I) to 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.

[0067] [Resin containing a structural unit derived from a carboxylate represented by formula (I)] The resin of the present invention is a resin (hereinafter sometimes referred to as "resin (A)") containing a structural unit derived from a carboxylate represented by formula (I) (hereinafter sometimes referred to as "structural unit (I)"). As an example of the structural unit (I), "structural unit (I-1)" is shown below. TIFF0007691875000042.tif79158[wherein R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , m1, m2, m3, m4, m5, m6, m7, m8, m9, X 10 , L 10 , X 4 , X 0 have the same meanings as described above.] R 1a , R 2a , R 3aEach independently represents a group represented by the formula (4a-1). The formula (4a-1) represents a state in which the double bond of CH 2 =C-R 10 contained in the group represented by the formula (4a) is cleaved. The structural unit (I-1) was a structural unit in which all of R 1 , R 2 , R 3 in the carboxylate represented by the formula (I) were cleaved, but the structural unit (I) does not necessarily require all of R 1 , R 2 , R 3 to be cleaved, and it is sufficient that any one of R 1 , R 2 , R 3 is cleaved like the group represented by the formula (4a-1). The resin (A) may be a homopolymer containing one kind of structural unit (I) or a copolymer containing two or more kinds of structural units (I). The content of the structural unit (I) is usually 0.1 to 100 mol%, preferably 0.5 to 50 mol%, more preferably 0.8 to 30 mol%, and still more preferably 1 to 10 mol% with respect to the total amount of the resin (A).

[0068] In addition to the structural unit (I), the resin (A) may further contain a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)"). Here, the "acid-labile group" has a leaving group, and upon contact with an acid, the leaving group is eliminated, and the constituent unit is converted into a constituent unit having a hydrophilic group (for example, a hydroxy group or a carboxy group). 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)"), other structural units (hereinafter sometimes referred to as "structural unit (t)"), and structural units known in the art.

[0069] 〈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)). TIFF0007691875000043.tif2298[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 bond.] TIFF0007691875000044.tif2278[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 -CH 2 - 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.]

[0070] Examples of the alkyl group for R a1 , R a2 and R a3 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, and the like. Ra1 , R a2 and R a3 Examples of the alkenyl group in R, R, and R include ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, isooctenyl group, and nonenyl group. R a1 , R a2 and R a3 The alicyclic hydrocarbon group in R, R, and R may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and 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 R, R, and R is preferably 3 to 16. TIFF0007691875000045.tif10159R a1 , R a2 and R a3 Examples of the aromatic hydrocarbon group in R, R, and R include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, and 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, etc. Preferably, ma is 0 and na is 1. R a1 and R a2 When R and R are bonded to each other to form an alicyclic hydrocarbon group, -C(R a1 )(Ra2 )(R a3 ) includes the following groups. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * represents a bond to -O-. TIFF0007691875000046.tif35157

[0071] R a1’ 、R a2’ and R a3’ Examples of the hydrocarbon group in 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 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, etc. R a2’ and R a3’ When R a1’ )(R a2’ )-X-R a3’ includes the following groups. * represents a bond. TIFF0007691875000047.tif18124 R a1’ and R a2’Among them, at least one is preferably a hydrogen atom. na' is preferably 0.

[0072] Examples of 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 group (1) include the following groups. * represents a bond. TIFF0007691875000048.tif119163

[0073] TIFF0007691875000049.tif38158

[0074] Specific examples of group (2) include the following groups. * represents a bond. TIFF0007691875000050.tif55153

[0075] 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.

[0076] Among the (meth)acrylic monomers having an acid-labile group, preferably, those having an alicyclic hydrocarbon group with 5 to 20 carbon atoms can be mentioned. 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 a resist composition, the resolution of the resist pattern can be improved.

[0077] As the structural unit derived from the (meth)acrylic monomer having the group (1), preferably, a structural unit represented by the formula (a1-0) (hereinafter, may be referred to as the structural unit (a1-0)), a structural unit represented by the formula (a1-1) (hereinafter, may be referred to as the structural unit (a1-1)), or a structural unit represented by the formula (a1-2) (hereinafter, may be referred to as the structural unit (a1-2)) can be mentioned. More preferably, it is at least one structural unit selected from the group consisting of the structural unit (a1-1) and the structural unit (a1-2). These may be used alone or in combination of two or more. TIFF0007691875000051.tif46149 [In the formula (a1-0), the formula (a1-1), and the formula (a1-2), L a01 、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 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 combining these. R a6 and R a7each 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.

[0078] R a01 , R a4 and R a5 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. L a01 , L a1 and L a2 is preferably an oxygen atom or -O-(CH 2 ) k01 It is -CO-O- (wherein k01 is preferably an integer of any one of 1 to 4, more preferably 1), and more preferably an oxygen atom. R a02 , R a03 and R a04 The alkyl group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group, and the combination thereof in the formula (1) are R a1 , R a2 and R a3 Examples of the groups include the same groups as those listed in the above. R a6 and R a7 The alkyl group, alkenyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and combinations thereof in the formula (1) include R a1 , R a2 and R a3 Examples of the groups are the same as those listed in R a02 , R a03 , and R a04 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R a6 and R a7The alkyl group herein is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group or a t-butyl group, and still more preferably an ethyl group, an isopropyl group or a t-butyl group. R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms of the alicyclic hydrocarbon group of R a02 , R a03 , R a04 , R a6 and R a7 is preferably 5 to 12, and more preferably 5 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 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 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, and 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, and 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, and 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, and 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, and 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.

[0079] Examples of the structural unit (a1-0) include a structural unit represented by any of Formula (a1-0-1) to Formula (a1-0-18) and a structural unit in which the methyl group corresponding to R in the structural unit (a1-0) is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group. 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) is preferable. a01 Examples thereof include a structural unit in which the methyl group corresponding to R is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group. 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) is preferable. TIFF0007691875000052.tif96164

[0080] Examples of the structural unit (a1-1) include a structural unit derived from a monomer described in JP-A-2010-204646. Among them, a structural unit represented by any of Formula (a1-1-1) to Formula (a1-1-7) and a structural unit in which the methyl group corresponding to R in the structural unit (a1-1) is replaced with a hydrogen atom are preferable, and a structural unit represented by any of Formula (a1-1-1) to Formula (a1-1-4) is more preferable. a4 Examples thereof include a structural unit in which the methyl group corresponding to R is replaced with a hydrogen atom. A structural unit represented by any of Formula (a1-1-1) to Formula (a1-1-4) is more preferable. TIFF0007691875000053.tif39167

[0081] Examples of the structural unit (a1-2) include a structural unit represented by any of Formula (a1-2-1) to Formula (a1-2-14) and a structural unit in which the methyl group corresponding to R in the structural unit (a1-2) is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group. A 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. a5 Examples thereof include a structural unit in which the methyl group corresponding to R is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group. A 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. TIFF0007691875000054.tif67163

[0082] When the resin (A) contains the structural unit (a1-0) and / or 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 90 mol%, more preferably 20 to 85 mol%, still more preferably 25 to 70 mol%, and even more preferably 30 to 70 mol% based on all the structural units of the resin (A).

[0083] 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 sometimes referred to as "structural unit (a1-4)"). TIFF0007691875000055.tif5374[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 Ra35 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and 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 a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -C-O- to which they are bonded, and -CH 2 - in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-.]

[0084] R a32 and R a33 Examples of the halogen atom in R R a32 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R 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 R R a33Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy 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 a33 Examples 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 a33 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 methoxyethyl group or an ethoxyethyl group. R a33 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, and more preferably an acetyl group. R a33 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, and more preferably an acetyloxy group. R a33is 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.

[0085] *-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- includes. Among them, *-CO-O-, *-CO-O-A a32 -CO-O- or *-O-A a32 -CO-O- is preferable.

[0086] 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, a 2-methylbutane-1,4-diyl group and the like. A a32 is preferably a methylene group or an ethylene group.

[0087] 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-CH 2 -CO-O-, and even more preferably a single bond or *-CO-O-.

[0088] la is preferably 0, 1 or 2, more preferably 0 or 1, and still more preferably 0. R a34 、R a35 and R a36 Examples of the hydrocarbon group for R Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. 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). TIFF0007691875000056.tif10151 Examples 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 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 and the like), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group and the like), aryl-cycloalkyl groups such as phenylcyclohexyl group and the like. In particular, R a36 Examples of R

[0089] R a34 is preferably a hydrogen atom. Ra35 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, more preferably a methyl group or an ethyl group. R a36 The hydrocarbon group of 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, more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic aliphatic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. R a36 The alkyl group and the alicyclic hydrocarbon group in are preferably unsubstituted. R a36 The aromatic hydrocarbon group in preferably has an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.

[0090] -OC(R a34 )(R a35 )-O-R a36 reacts with an acid (for example, p-toluenesulfonic acid) and eliminates 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, more preferably bonded to the p-position.

[0091] Examples of the structural unit (a1-4) include structural units derived from the monomers described in JP-A-2010-204646. Preferably, the structural units represented by formula (a1-4-1) to formula (a1-4-18) and the structural unit in (a1-4) where the hydrogen atom corresponding to R a32 is replaced by a halogen atom, a haloalkyl group, or an alkyl group are mentioned, and more preferably, the 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) are mentioned. TIFF0007691875000057.tif99157

[0092] When the resin (A) has the structural unit (a1-4), its content is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, still more preferably 20 to 85 mol%, still more preferably 20 to 70 mol%, and particularly preferably 20 to 60 mol% based on the total of all the structural units of the resin (A).

[0093] Examples of the structural unit derived from the (meth)acrylic monomer having the group (2) include the structural unit represented by the formula (a1-5) (hereinafter sometimes referred to as "structural unit (a1-5)"). TIFF0007691875000058.tif4253In the formula (a1-5), R a8 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. Z a1 represents a single bond or *-(CH 2 ) h3 -CO-L 54 -, h3 represents an integer of 1 to 4, and * represents a bond with L 51 . L 51 , L 52 , L 53 and L 54 each independently represents -O- or -S-. s1 represents an integer of 1 to 3. s1' represents an integer of 0 to 3.

[0094] 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 the 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 It is preferable that one of them is -O- and the other is -S-. s1 is preferably 1. s1' is preferably any integer from 0 to 2. Z a1 is a single bond or *-CH 2 -CO-O- is preferable.

[0095] Examples of the structural unit (a1-5) include structural units derived from the 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. TIFF0007691875000059.tif31129

[0096] 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).

[0097] In addition, examples of the structural unit (a1) include the following structural units. TIFF0007691875000060.tif27161

[0098] When the resin (A) contains structural units such as (a1-3-1) to (a1-3-7) above, its content is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, still more preferably 20 to 85 mol%, even more preferably 20 to 70 mol%, and particularly preferably 20 to 60 mol% based on all the structural units of the resin (A).

[0099] 〈Structural unit (s)〉 The structural unit(s) is / are derived from monomers having no acid-labile group (hereinafter sometimes referred to as "monomer(s)"). As the monomer(s) from which the structural unit(s) is / are derived, monomers 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.

[0100] 〈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 the 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 contained alone or in two or more kinds.

[0101] 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)"). TIFF0007691875000061.tif4349[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 a51represents 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 is a single bond or *-X a51 -(A a52 -X a52 ) nb - and * 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 any integer from 0 to 4. When mb is any integer of 2 or more, a plurality of R a51 may be the same as or different from each other.

[0102] R a50 and R a51 Examples of the halogen atom in 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 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 a50is 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 a51 Examples of the alkyl group in a51 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 still more preferably a methyl group. R a51 Examples of the alkoxy group in a51 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 still more preferably a methoxy group. R a51 Examples of the alkoxyalkyl group in a51 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 still more preferably a methoxymethyl group. R a51 Examples of the alkoxyalkoxy group in a51 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 in a51 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 a51Examples 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.

[0103] *-X a51 -(A a52 -X a52 ) nb Examples of - include *-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.

[0104] 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.

[0105] A a50is a single bond, *-CO-O- or *-CO-OA a52 -CO-O- is preferred, and a single bond, *-CO-O- or *-CO-O-CH 2 It is more preferably -CO-O-, and further preferably a single bond or *-CO-O-.

[0106] 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- or para-position of the benzene ring, and more preferably to the para-position.

[0107] Examples of the structural unit (a2-A) include structural units derived from monomers described in JP-A-2010-204634 and JP-A-2012-12577. The structural unit (a2-A) includes structural units represented by formulae (a2-2-1) to (a2-2-16) and R in the structural unit (a2-A) in the structural units represented by formulae (a2-2-1) to (a2-2-16). a50 The structural unit (a2-A) includes a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6), a structural unit represented by formula (a2-2-8), a structural unit represented by formula (a2-2-12) to (a2-2-14), and a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6), a structural unit represented by formula (a2-2-8), and a structural unit represented by formula (a2-2-12) to (a2-2-14), a50It is preferable that the structural unit in which the methyl group corresponding to R is replaced with a hydrogen atom is a structural unit represented by the formula (a2-2-3), a structural unit represented by the formula (a2-2-8), a structural unit represented by the formulas (a2-2-12) to (a2-2-14), and a structural unit represented by the formula (a2-2-3) or a structural unit represented by the formula (a2-2-8), a structural unit represented by the formulas (a2-2-12) to (a2-2-14), and in the structural unit (a2-A), R a50 More preferably, it is a structural unit in which the methyl group corresponding to R 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 It is even more preferable that the methyl group corresponding to R is replaced with a hydrogen atom. TIFF0007691875000062.tif53169

[0108] When the resin (A) contains the structural unit (a2-A), the content of the structural unit (a2-A) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, still more preferably 15 to 65 mol%, and even more preferably 20 to 65 mol% based on 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, the structural unit (a2-A) can be incorporated into the resin (A) by treating with an alkali such as tetramethylammonium hydroxide.

[0109] 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)"). TIFF0007691875000063.tif4156 In the formula (a2-1), L a3 represents -O- or *-O-(CH 2 ) k2 -CO-O-, k2 represents any integer from 1 to 7. * represents a bond 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 any integer from 0 to 10.

[0110] In formula (a2-1), L a3 is preferably -O-, -O-(CH 2 ) f1 -CO-O- (wherein f1 represents any integer from 1 to 4), and more preferably -O-. R a14 is preferably a methyl group. R a15 is preferably a hydrogen atom. R a16 is preferably a hydrogen atom or a hydroxy group. o1 is preferably any integer from 0 to 3, and more preferably 0 or 1.

[0111] Examples of the structural unit (a2-1) include structural units derived from the monomers described in JP-A-2010-204646. A structural unit represented by any of formulas (a2-1-1) to (a2-1-6) is preferred, a structural unit represented by any 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. TIFF0007691875000064.tif54150

[0112] When the resin (A) contains the structural unit (a2-1), its content is usually 1 to 45 mol%, preferably 1 to 40 mol%, more preferably 1 to 35 mol%, even more preferably 1 to 20 mol%, and even more preferably 1 to 10 mol% based on all the structural units of the resin (A).

[0113] <Structural unit (a3)> The lactone ring possessed by the structural unit (a3) may be a monocyclic ring such as a β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring and another ring. Preferably, a γ-butyrolactone ring, adamantanlactone ring, or bridged ring containing a γ-butyrolactone ring structure (for example, the structural unit represented by the following formula (a3-2)) can be mentioned.

[0114] The structural unit (a3) is preferably a structural unit represented by formula (a3-1), formula (a3-2), formula (a3-3), or formula (a3-4). These may be contained alone or in combination of two or more. TIFF0007691875000065.tif51164[In formula (a3-1), formula (a3-2), formula (a3-3), and formula (a3-4), L a4 、L a5 and L a6 each independently represents a group represented by -O- or *-O-(CH 2 ) k3 -CO-O- (where k3 represents an integer from 1 to 7). L a7 represents -O-, *-O-L a8 -O-, *-O-L a8 -CO-O-, *-O-L a8 -CO-O-L a9 -CO-O- or *-O-L a8 -O-CO-L a9 -O-. 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 is -CH2 - or represents 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.

[0115] R a21 、R a22 、R a23 and R a25 Examples of the aliphatic hydrocarbon group in R R a24 include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and tert-butyl group. R a24 Examples of the alkyl group in R R a24Examples of the alkyl group having a halogen atom in [description] 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, and the like. L a8 and L a9 Examples of the alkanediyl group in [description] 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, and the like.

[0116] In formulas (a3-1) to (a3-3), L a4 ~L a6 are each independently preferably -O- or, *-O-(CH 2 ) k3 -CO-O- where k3 is an integer from 1 to 4, more preferably -O- and, *-O-CH 2 -CO-O-, even more preferably an oxygen atom. R a18 ~R a21 are 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 from 0 to 2, more preferably 0 or 1.

[0117] 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, even more preferably a hydrogen atom or a methyl group. Ra25 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-CH 2 -CO-O- or -O-C 2 H 4 -CO-O-. w1 is preferably any integer from 0 to 2, more preferably 0 or 1. In particular, formula (a3-4) is preferably formula (a3-4)'. TIFF0007691875000066.tif4051(wherein R a24 and L a7 represent the same meaning as described above.)

[0118] 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 by hydrogen atoms are preferred.

[0119] TIFF0007691875000067.tif115165

[0120] 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% with respect to all the structural units of the resin (A). In addition, the content rate of structural unit (a3-1), structural unit (a3-2), structural unit (a3-3) or structural unit (a3-4) is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, still more preferably 10 to 50 mol% with respect to all the structural units of resin (A).

[0121] 〈Structural unit (a4)〉 Examples of the structural unit (a4) include the following structural units. TIFF0007691875000068.tif3066[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having a fluorine atom with 1 to 24 carbon atoms, and -CH 2 - in the saturated hydrocarbon group may be replaced by -O- or -CO-.] R 42 The saturated hydrocarbon group represented by includes a chain hydrocarbon group, a monocyclic or polycyclic alicyclic hydrocarbon group, and a group formed by combining these, etc.

[0122] 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 a bond). TIFF0007691875000069.tif11159Examples of the group formed by combination include a group formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups, and -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group-alkyl group, etc.

[0123] Examples of the structural unit (a4) include at least one structural unit 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). TIFF0007691875000070.tif4652[In formula (a4-0), R 5 represents a hydrogen atom or a methyl group. L 4a represents a single bond or a divalent aliphatic saturated hydrocarbon 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 6 represents a hydrogen atom or a fluorine atom.]

[0124] L 4a Examples of the divalent aliphatic saturated hydrocarbon group in L include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group, and branched alkanediyl groups such as an ethane-1,1-diyl group, a propane-1,2-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, and a 2-methylpropane-1,2-diyl group. L 3aExamples of the perfluoroalkanediyl group in [description] include a difluoromethylene group, a perfluoroethylene group, a perfluoropropane-1,1-diyl group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, a perfluoropropane-2,2-diyl group, a perfluorobutane-1,4-diyl group, a perfluorobutane-2,2-diyl group, a perfluorobutane-1,2-diyl group, a perfluoropentane-1,5-diyl group, a perfluoropentane-2,2-diyl group, a perfluoropentane-3,3-diyl group, a perfluorohexane-1,6-diyl group, a perfluorohexane-2,2-diyl group, a perfluorohexane-3,3-diyl group, a perfluoroheptane-1,7-diyl group, a perfluoroheptane-2,2-diyl group, a perfluoroheptane-3,4-diyl group, a perfluoroheptane-4,4-diyl group, a perfluorooctane-1,8-diyl group, a perfluorooctane-2,2-diyl group, a perfluorooctane-3,3-diyl group, a perfluorooctane-4,4-diyl group, and the like. L 3a Examples of the perfluorocycloalkanediyl group in [description] include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, a perfluoroadamantanediyl group, and the like.

[0125] 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.

[0126] 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. 5 are mentioned. TIFF0007691875000071.tif95165

[0127] TIFF0007691875000072.tif3960In 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 -CH 2 - 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. TIFF0007691875000073.tif1384[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 bond, and the * on the right is a bond with -O-CO-R a42 .

[0128] R a42 Examples of the saturated hydrocarbon group in R include a chain saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and a group formed by combining these. 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 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 a bond). Examples of the group formed by the combination include a group 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.

[0129] R a42 Examples of the substituent that R may have include at least one selected from 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. TIFF0007691875000075.tif965[In the formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-. A a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. * represents the bond with R a42 . However, in R a42 -X a43 -A a45 , when R a42 does not have a halogen atom, A a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which has at least one halogen atom.

[0130] A a45 Examples of the aliphatic hydrocarbon group in [description] 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 a bond). Examples of the group formed by the combination of TIFF0007691875000076.tif11159 include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups, such as -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group-alkyl group, etc.

[0131] R a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, more preferably an alkyl group having a halogen atom and / or an aliphatic hydrocarbon group having a group represented by formula (a-g3). R a42 When R is an aliphatic hydrocarbon group having a halogen atom, it is preferably an aliphatic 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 a42When R is an aliphatic hydrocarbon group having a group represented by the formula (a-g3), including the number of carbon atoms contained in the group represented by the formula (a-g3), a42 the total number of carbon atoms of R 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.

[0132] R a42 When R is an aliphatic hydrocarbon having a group represented by the formula (a-g3), a42 R is more preferably a group represented by the formula (a-g2). TIFF0007691875000077.tif879[In the formula (a-g2), A a46 represents a divalent aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. X a44 represents **-O-CO- or **-CO-O- (** represents a bond to A a46 ). A a47 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. However, the total number of carbon atoms of A a46 , A a47 and X a44 is 18 or less, and at least one of A a46 and A a47 has at least one halogen atom. * represents a bond to a carbonyl group.]

[0133] A a46 The number of carbon atoms of the aliphatic hydrocarbon group of A is preferably 1 to 6, more preferably 1 to 3. A a47 The number of carbon atoms of the aliphatic hydrocarbon group of A is preferably 4 to 15, more preferably 5 to 12, and A a47 is more preferably a cyclohexyl group or an adamantyl group.

[0134] A preferred structure of the group represented by the formula (a-g2) is the following structure (* is a bond to a carbonyl group). TIFF0007691875000078.tif13161

[0135] A a41 Examples of the alkanediyl group in the formula (I) 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 butane-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. A a41 Examples of the substituent in the alkanediyl group include a hydroxy group and an alkoxy group 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 further preferably an ethylene group.

[0136] 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 a linear or branched alkanediyl group, a monocyclic divalent alicyclic hydrocarbon group, and a group formed by combining an alkanediyl group and a divalent alicyclic hydrocarbon group, etc. Specific examples 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 1-methylpropane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 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 the formula (1) include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. It is preferred that s is 0.

[0137] In the group represented by formula (a-g1), X a42Examples of the group being -O-, -CO-, -CO-O- or -O-CO- include the following groups and the like. In the following examples, * and ** each represent a bond, and ** is a bond with -O-CO-R a42 and is a bond with. TIFF0007691875000079.tif54162

[0138] Examples of the structural unit represented by formula (a4-1) 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 represented by formula (a4-1) is replaced by a hydrogen atom. a41 TIFF0007691875000080.tif167143

[0139] TIFF0007691875000081.tif66133

[0140] As the structural unit represented by formula (a4-1), the structural unit represented by formula (a4-2) is preferred. TIFF0007691875000082.tif4366[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 -CH 2 - 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 number of carbon atoms of L 44 and R f6 is 21.]

[0141] The alkanediyl group having 1 to 6 carbon atoms of L 44 includes the same groups as those exemplified for the alkanediyl group in A a41 . R f6 The saturated hydrocarbon group of a42 includes the same groups as those exemplified for R ​L 44 As the C1-C6 alkanediyl group in, a C2-C4 alkanediyl group is preferred, and an ethylene group is more preferred.

[0142] Examples of the structural unit represented by the formula (a4-2) include the structural units represented by the formulas (a4-1-1) to (a4-1-11), respectively. R in the structural unit (a4-2) f5 The structural unit in which the methyl group corresponding to is replaced by a hydrogen atom is also included as the structural unit represented by the formula (a4-2).

[0143] Examples of the structural unit (a4) include the structural unit represented by the formula (a4-3). TIFF0007691875000083.tif5771 [In the formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 represents a C1-C6 alkanediyl group. 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 bond 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.]

[0144] L 5 Examples of the alkanediyl group in include the same groups as those exemplified for the alkanediyl group in the divalent saturated hydrocarbon group of A a41 . A f13The divalent saturated hydrocarbon group which may have a fluorine atom is preferably a divalent aliphatic 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 aliphatic hydrocarbon group which may have a fluorine atom include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group; perfluoroalkanediyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluorobutanediyl group and perfluoropentanediyl group. The divalent alicyclic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic group include cyclohexanediyl group and perfluorocyclohexanediyl group. Examples of the polycyclic group include adamantandiyl group, norbornanediyl group, perfluoroadamantandiyl group. A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom of a42 include the same groups as those exemplified by R. Among them, fluorinated alkyl 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 are preferred.

[0145] In formula (a4-3), L 5 is preferably an ethylene group. A f13 The divalent saturated hydrocarbon group of is preferably a group containing 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 of is preferably a group containing 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 containing 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 containing 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.

[0146] Examples of the structural unit represented by formula (a4-3) include structural units represented by formulas (a4-1'-1) to (a4-1'-11), respectively. The structural unit in which the methyl group corresponding to R f7 in the structural unit (a4-3) is replaced by a hydrogen atom is also included as the structural unit represented by formula (a4-3).

[0147] Examples of the structural unit (a4) also include the structural unit represented by formula (a4-4). TIFF0007691875000084.tif4466[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 is -(CH 2 ) j1 -, -(CH 2 ) j2 -O-(CH 2 ) j3 - or -(CH 2 ) j4 -CO-O-(CH 2 ) j5 -. j1 to j5 each independently represent an integer from 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom.

[0148] R f22 The saturated hydrocarbon group of is the same as the saturated hydrocarbon group represented by R a42 Examples of the saturated hydrocarbon group represented by R f22 is preferably an alkyl group having 1 to 10 carbon atoms and having a fluorine atom or an alicyclic hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms and having a fluorine atom, and even more preferably an alkyl group having 1 to 6 carbon atoms and having a fluorine atom.

[0149] In formula (a4-4), A f21 is preferably -(CH 2 ) j1 -, more preferably an ethylene group or a methylene group, and even more preferably a methylene group.

[0150] 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 f21 in the structural unit (a4-4) is replaced by a hydrogen atom. TIFF0007691875000085.tif80148

[0151] 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).

[0152] 〈Structural unit (a5)〉 Examples of the non-leaving hydrocarbon group of the structural unit (a5) include a group having a linear, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group. Examples of the structural unit (a5) include the structural unit represented by formula (a5-1). 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 55 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH 2 - contained in the saturated hydrocarbon group may be replaced with -O- or -CO-.

[0153] R 52 The alicyclic hydrocarbon group in R 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. L 55 Examples of the divalent saturated hydrocarbon group in L 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 cycloalkane diyl groups such as cyclopentane diyl group and cyclohexane diyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include adamantane diyl group and norbornane diyl group.

[0154] L 55 Examples of the group in which -CH 2 - contained in the divalent saturated hydrocarbon group represented by - is replaced by -O- or -CO- include, for example, the groups represented by formula (L1-1) to formula (L1-4). In the following formulas, * and ** each represent a bond, and * represents a bond to an oxygen atom. TIFF0007691875000087.tif18166 In formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents a bond to 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, L x5 , L x6 and L x7 have a total carbon number of 15 or less. In formula (L1-4), L x8 and L x9 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.

[0155] 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.

[0156] Examples of the group represented by the formula (L1-1) include the following divalent groups. TIFF0007691875000088.tif52135

[0157] Examples of the group represented by the formula (L1-2) include the following divalent groups. TIFF0007691875000089.tif23130

[0158] Examples of the group represented by the formula (L1-3) include the following divalent groups. TIFF0007691875000090.tif15147

[0159] Examples of the group represented by the formula (L1-4) include the following divalent groups. TIFF0007691875000091.tif26114

[0160] L 55 is preferably a single bond or a group represented by the formula (L1-1).

[0161] Examples of the structural unit (a5-1) include the following structural units and the structural units in the following structural units where the methyl group corresponding to R in the structural unit (a5-1) is replaced by a hydrogen atom. 51 are mentioned. TIFF0007691875000092.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). 〈Structural unit (a6)〉 The structural unit (a6) is a structural unit having a -SO 2 - group, and -SO2 Preferably has a - group as a side chain. -SO 2 The structural unit having a - group may have a linear structure having a -SO 2 - group, or may have a branched structure having a -SO 2 - group, or may have a cyclic structure (monocyclic and polycyclic structures) having a -SO 2 - group. Preferably, it is a structural unit having a cyclic structure having a -SO 2 - group, and more preferably, it is a structural unit having a cyclic structure (sultone ring) containing -SO 2 -O-.

[0162] Examples of the sultone ring include rings represented by the following formula (T 1 -1), formula (T 1 -2), formula (T 1 -3) and formula (T 1 -4). 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 -SO 2 -O- as an atomic group constituting the ring, and examples include rings represented by formula (T 1 -1) and formula (T 1 -2). The sultone ring may further contain a heteroatom in addition to -SO 1 -O- as an atomic group constituting the ring, as in the ring represented by formula (T 2 -2). Examples of the heteroatom include an oxygen atom, a sulfur atom or a nitrogen atom, and preferably an oxygen atom. TIFF0007691875000093.tif3287

[0163] The sultone ring may have a substituent, and examples of the substituent include a halogen atom or an alkyl group having 1 to 12 carbon atoms which may have 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, etc.

[0164] 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, it is 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 included. 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 included, and more preferably a methoxycarbonyl group is included. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.

[0165] From the viewpoint that it is easy to produce the monomer leading to the structural unit (a6), a sultone ring having no substituent is preferred. As the sultone ring, a ring represented by the following formula (T1’) is preferred. TIFF0007691875000094.tif3272[In the formula (T1’), 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. 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 thereof are the same as those of the substituent of the sultone ring, and an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group is preferred.

[0166] As the sultone ring, a ring represented by the formula (T1) is more preferred. TIFF0007691875000095.tif3249[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 an integer from 0 to 9. When m is 2 or more, a plurality of Rs 8 may be the same or different. The bonding site is at an arbitrary position.]

[0167] R 8 is of the same kind as R 41 and the like can be mentioned. ma in formula (T1’) and m in formula (T1) are preferably 0 or 1, more preferably 0.

[0168] Examples of the ring represented by formula (T1’) and the ring represented by formula (T1) include the following rings. The bonding site is at an arbitrary position. TIFF0007691875000096.tif53159

[0169] The structural unit having a sultone ring preferably has the following group. * in the following group represents the bonding site. TIFF0007691875000097.tif51161

[0170] -SO 2 The structural unit having a - 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 leading to the structural unit (a6) is preferably a monomer having an ethylenically unsaturated bond, more preferably a (meth)acrylic monomer.

[0171] The structural unit (a6) is preferably a structural unit represented by formula (Ix). TIFF0007691875000098.tif4958[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 is an oxygen atom, -N(Rc ) - represents an oxygen atom or a sulfur atom. A x represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH 2 - 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.

[0172] 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. Rx 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.

[0173] A x Examples of the divalent saturated hydrocarbon group of x include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and combinations of 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, 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, 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, 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, adamantane-2,6-diyl group, etc. are included.

[0174] 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 a specific bonding position are preferred.

[0175] Examples of the structural unit (a6) include the following structural units. TIFF0007691875000099.tif100160

[0176] 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 preferred, and the structural units represented by formula (a6-1), formula (a6-2), formula (a6-7) and (a6-8) are more preferred. 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).

[0177] <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.

[0178] The structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain is preferably a structural unit represented by formula (II-2-A'). TIFF0007691875000100.tif35104[In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH contained in the saturated hydrocarbon group 2- may be replaced by -O-, -S- or -CO-, and the 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 the 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.

[0179] R III3 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. R III3 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 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, etc. A X1Examples of the C1-C6 perfluoroalkyl group which may be substituted include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluoro tert-butyl group, perfluoropentyl group, perfluorohexyl group and the like. X III3 Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by III3 include linear or branched alkanediyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and combinations thereof may also be used. 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 and the like. -CH 2 Examples of those in which - 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 -CH- in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- is each 17 or less. In the following formulas, * and ** represent bonding sites, and * represents a bond to A. 2 - is replaced by -O-, -S- or -CO- are each 17 or less. In the following formulas, * and ** represent bonding sites, and * represents a bond to A x1 and the bond to. TIFF0007691875000101.tif145161

[0180] 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 8 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

[0181] ZA in formula (II-2-A’) + is the same as the cation Z1 in the salt represented by formula (B1). + Examples thereof include the same ones.

[0182] The structural unit represented by formula (II-2-A’) is preferably the structural unit represented by formula (II-2-A). TIFF0007691875000102.tif38108 [In formula (II-2-A), R III3 、X III3 and ZA + represent the same meanings 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 Qb Examples of the perfluoroalkyl group having 1 to 6 carbon atoms represented by the formula include the aforementioned Q b1 and the same perfluoroalkyl groups having 1 to 6 carbon atoms represented by the formula can be mentioned.

[0183] The structural unit represented by formula (II-2-A) is preferably the structural unit represented by formula (II-2-A-1). TIFF0007691875000103.tif5577 [In formula (II-2-A-1), R III2 、R III3 、R III4 、Q a 、Q b and ZA + have the same meanings 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, and the -CH 2 - contained in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-, and the 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 the formula 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 the formula include the same divalent saturated hydrocarbon groups as those represented by X III3 represented by the formula.

[0184] As the structural unit represented by formula (II-2-A-1), the structural unit represented by formula (II-2-A-2) is more preferable. TIFF0007691875000104.tif5287 [In formula (II-2-A-2), R III3 、R III5 and ZA + have the same meaning as described above. m and nA each independently represent 1 or 2.

[0185] Examples of the structural unit represented by the formula (II-2-A’) include the following structural units, R III3 wherein a group corresponding to the methyl group of R is replaced with 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 International Publication No. 2012 / 050015. ZA + represents an organic cation. TIFF0007691875000105.tif86163

[0186] 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). TIFF0007691875000106.tif3691 [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, etc. R II2 and R II3Examples 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 groups. R II4 Examples of the halogen atom represented by 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 include the same ones as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by . a8 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by include the same ones as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by . A II1 Examples of the divalent linking group represented by include, for example, a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH 2 - contained in the divalent saturated hydrocarbon group may be replaced by -O-, -S- or -CO-. Specifically, examples of the divalent saturated hydrocarbon group represented by include the same ones as the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by . III3 Examples of the divalent saturated hydrocarbon group represented by include the same ones as the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by .

[0187] Examples of the structural unit containing a cation in formula (II-1-1) include a structural unit represented by the following and a structural unit in which a group corresponding to the methyl group of R II4 is replaced by a hydrogen atom, a fluorine atom, a trifluoromethyl group, etc. TIFF0007691875000107.tif84130

[0188] A - Examples of the organic anion represented by include a sulfonate anion, a sulfonylimide anion, a sulfonylmethide anion, and a carboxylate anion. Examples of the organic anion represented by are preferably sulfonate anions, and more preferably anions contained in the salts represented by formula (B1) described later. - Examples of the sulfonylimide anion include the following. Examples of the sulfonylimide anion include the following. TIFF0007691875000108.tif38135 Examples of the sulfonylmethide anion include the following. TIFF0007691875000109.tif31127 Examples of the carboxylic acid anion include the following. TIFF0007691875000110.tif43155

[0189] Examples of the structural unit represented by formula (II-1-1) include the structural units represented below. TIFF0007691875000111.tif87149

[0190] 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).

[0191] The resin (A) may have structural units other than the above-described structural units, and examples of such structural units include structural units well-known in the art.

[0192] The resin (A) is preferably a resin composed of the structural unit (I), the structural unit (a1), and the structural unit (s), that is, a copolymer of the carboxylate (I), the monomer (a1), and the monomer (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 at least two kinds selected from the group consisting of the structural unit (a1-1) and 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 the structural unit (a2-1) or the structural unit (a2-A). The structural unit (a3) is preferably at least one selected from the group consisting of the structural unit represented by formula (a3-1), the structural unit represented by formula (a3-2), and the structural unit represented by formula (a3-4).

[0193] 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 the monomers that lead to these structural units. The content ratio 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 the value determined by gel permeation chromatography under the conditions described in the examples.

[0194] [Resist composition] The resist composition of the present invention contains at least a resin and an acid generator. The resist composition of the present invention may contain a resin (resin (A)) containing the structural unit (I) or an acid generator containing the carboxylate (I). The resist composition of the present invention may contain both the resin (A) and an acid generator containing the carboxylate (I). The resist composition of the present invention is preferably a resist composition containing at least the resin (A). It may contain two or more kinds of the resin (A). The resist composition of the present invention preferably further contains an acid generator (hereinafter sometimes referred to as "acid generator (B)"), a quencher (hereinafter sometimes referred to as "quencher (C)") and / or a solvent (hereinafter sometimes referred to as "solvent (E)") known in the resist field.

[0195] [Resin other than resin (A)] The resist composition of the present invention may use a resin other than the resin (A) in combination. For example, when the resist composition does not contain an acid generator containing the carboxylate (I), the resist composition can contain other resins in addition to the resin (A). Also, for example, when the resist composition contains an acid generator containing the carboxylate (I), the resist composition can contain the resin (A) and / or other resins. Examples of other resins include resins containing the above-described structural unit (a1) (hereinafter sometimes referred to as resin (AA). However, they do not contain structural unit (I).)

[0196] Examples of other resins also include resins containing structural unit (a4) or structural unit (a5) (however, they do not contain structural unit (I) and structural unit (a1). Hereinafter sometimes referred to as "resin (X)"). As resin (X), a resin containing structural unit (a4) is particularly preferred. In resin (X), the content of structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 45 mol% or more based on the total of all structural units of resin (X). Examples of structural units that resin (X) may further have include structural unit (a1), structural unit (a2), structural unit (a3), and structural units derived from other known monomers. Among them, resin (X) is preferably a resin composed of only structural unit (a4) and / or structural unit (a5). Each structural unit constituting 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 monomers that induce these structural units. The content of each structural unit of resin (X) can be adjusted by the amount of monomers used in the polymerization. The weight average molecular weight of 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 measuring means for the weight average molecular weight of resin (X) is the same as that for resin (A).

[0197] When the resist composition of the present invention contains resin (X), its content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, even 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 resin (A).

[0198] 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, based on the solid content of the resist composition. When a resin other than the resin (A) is included, 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, based on the solid content of the resist composition. 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. The solid content of the resist composition and the content rate of the resin with respect to the solid content can be measured by known analysis means such as liquid chromatography or gas chromatography.

[0199] <Acid generator (B)> As the acid generator (B), either a nonionic type or an ionic type may be used. Examples of the nonionic acid generator include sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxy ketone, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane), etc. Representative examples of the ionic acid generator include onium salts containing an onium cation (e.g., diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of the anion of the onium salt include sulfonic acid anion, sulfonylimide anion, sulfonylmethide anion, etc.

[0200] As the acid generator (B), compounds that generate an acid by radiation described in, for example, 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, U.S. Patent No. 3,779,778, U.S. Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc. can be used. Also, compounds produced by known methods may be used. The acid generator (B) may be used in combination of two or more.

[0201] 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)"). TIFF0007691875000112.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 -CH 2 - 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 -CH 2 - contained in the alicyclic hydrocarbon group may be replaced by -O-, -SO 2 - or -CO-. Z + represents an organic cation.]

[0202] Q b1 and Q b2 Examples of the perfluoroalkyl group represented by 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.

[0203] L b1Examples of the divalent saturated hydrocarbon group in [compound name] include linear alkanediyl groups, branched alkanediyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and groups formed by combining two or more of these groups. 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, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, and heptadecane-1,17-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 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, 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, adamantane-2,6-diyl group, etc.

[0204] L b1 Examples of the group in which -CH 2 - contained in the divalent saturated hydrocarbon group represented by [formula] 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.

[0205] TIFF0007691875000113.tif26117[In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH 2 - contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, the total number of carbon atoms of L b2 and L b3 is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH 2 - contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, the total number of carbon atoms of L b4 and L b5 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 a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH 2 - 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.

[0206] In the groups represented by formula (b1-1) to formula (b1-3), when -CH 2 - contained in the saturated hydrocarbon group is replaced by -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 .

[0207] 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 atom contained in the divalent saturated hydrocarbon group may be replaced by a fluorine atom. L b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a fluorine atom. L b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group, and -CH 2 - contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-.

[0208] L b1 As the group in which -CH 2 - contained in the divalent saturated hydrocarbon group represented by is replaced by -O- or -CO-, the group represented by formula (b1-1) or formula (b1-3) is preferable.

[0209] Examples of the group represented by formula (b1-1) include the groups represented by formulas (b1-4) to (b1-8). TIFF0007691875000114.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 -CH 2 - contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-. L b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, the total number of carbon atoms in L b9 and 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, the total number of carbon atoms in L b11 and L b12 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 -CH 2 - contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-. L b15represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, the total number of carbon atoms of L b13 ~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 -CH 2 - contained in the divalent saturated hydrocarbon group may be replaced with -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 the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, the total number of carbon atoms of L b16 ~L b18 is 19 or less.

[0210] 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 b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15is 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.

[0211] Examples of the group represented by the formula (b1-3) include the groups represented by the formulas (b1-9) to (b1-11). TIFF0007691875000115.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. -CH contained in the alkylcarbonyloxy group 2 - may be replaced with -O- or -CO-, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, L b19 and L b20 have a total carbon number of 23 or less. In the formula (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23represents 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. -CH 2 - in the alkylcarbonyloxy group may be replaced by -O- or -CO-, and the hydrogen atoms contained in the alkylcarbonyloxy group may be substituted with hydroxy groups. However, b21 L b22 and b23 L 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. -CH 2 - in the alkylcarbonyloxy group may be replaced by -O- or -CO-, and the hydrogen atoms contained in the alkylcarbonyloxy group may be substituted with hydroxy groups. However, b24 L b25 and b26 L

[0212] 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.

[0213] Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group and the like.

[0214] Examples of the group represented by formula (b1-4) include the following. TIFF0007691875000116.tif16154

[0215] Examples of the group represented by formula (b1-5) include the following. TIFF0007691875000117.tif68152

[0216] Examples of the group represented by formula (b1-6) include the following. TIFF0007691875000118.tif32164

[0217] Examples of the group represented by formula (b1-7) include the following. TIFF0007691875000119.tif57146

[0218] Examples of the group represented by formula (b1-8) include the following. TIFF0007691875000120.tif23150

[0219] Examples of the group represented by formula (b1-2) include the following. TIFF0007691875000121.tif31161

[0220] Examples of the group represented by formula (b1-9) include the following. TIFF0007691875000122.tif44137

[0221] Examples of the group represented by formula (b1-10) include the following. TIFF0007691875000123.tif92165

[0222] Examples of the group represented by formula (b1-11) include the following. TIFF0007691875000124.tif84164

[0223] Examples of the alicyclic hydrocarbon group represented by Y include groups represented by formula (Y1) to formula (Y11), formula (Y36) to formula (Y38). -CH contained in the alicyclic hydrocarbon group represented by Y 2 - is replaced by -O-, -SO 2 - or -CO-, the number thereof may be one or two or more. Examples of such groups include groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43). * represents the bonding site with L b1 and represents the bonding site with L TIFF0007691875000125.tif84167

[0224] The alicyclic hydrocarbon group represented by Y is preferably a group represented by any 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 still 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), formula (Y40), formula (Y42), formula (Y43), etc., the alkanediyl group between 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.

[0225] 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, -(CH 2 ) ja -CO-O-R b1a group or -(CH 2 ) 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 -CH 2 - contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -S(O) 2 -, 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.) and the like can be mentioned. As substituents of the alicyclic hydrocarbon group represented by Y, a halogen atom, a hydroxy group, an alkyl group having 1 to 16 carbon atoms which may be substituted by a hydroxy group (the -CH 2 - 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, -(CH 2 ) ja -CO-O-R b1 group or -(CH 2 ) 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 -CH 2 - contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SO 2 -, 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.) and the like can be mentioned.

[0226] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 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. -CH contained in the alkyl group 2 - is -O-, -SO 2Examples of the group replaced by -or -CO- etc. include an alkoxy group, an alkylsulfonyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, or a group combining these. 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, a dodecyloxy group and the like. The number of carbon atoms of the alkoxy group is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group and the like. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkoxycarbonyl group include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group and the like. The number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the alkylcarbonyl group include, for example, an acetyl group, a propionyl group, a butyryl group and the like. The number of carbon atoms of the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the alkylcarbonyloxy group include, for example, an acetyloxy group, a propionyloxy group, a butyryloxy group and the like. The number of carbon atoms of 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, for example, a group combining an alkoxy group and an alkyl group, a group combining an alkoxy group and an alkoxy group, a group combining an alkoxy group and an alkylcarbonyl group, a group 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. -CH contained in the alicyclic hydrocarbon group 2 - is replaced by -O-, -SO 2 - or -CO- etc. include the groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43).

[0227] Examples of Y include the following. TIFF0007691875000126.tif60165

[0228] TIFF0007691875000127.tif111166

[0229] 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. The -CH 2 - in - is -CO-, -SO 2 - or may be replaced by -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).

[0230] As the anion in the salt represented by formula (B1), anions represented by formula (B1-A-1) to formula (B1-A-59) [hereinafter may be 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. TIFF0007691875000128.tif87158

[0231] TIFF0007691875000129.tif117158

[0232] TIFF0007691875000130.tif125157

[0233] TIFF0007691875000131.tif129140

[0234] TIFF0007691875000132.tif111158

[0235] TIFF0007691875000133.tif56117Here, R i2 ~R i7is, 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 A4 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q b1 and Q b2 represent the same meaning as described above. Specific examples of the anion in the salt represented by the formula (B1) include the anions described in JP-A-2010-204646.

[0236] Preferred anions in the salt represented by the formula (B1) include the anions represented by the formula (B1a-1) to the formula (B1a-38), respectively. TIFF0007691875000134.tif203153

[0237] TIFF0007691875000135.tif166155

[0238] Among them, anions represented by any of the formula (B1a-1) to the formula (B1a-3), the formula (B1a-7) to the formula (B1a-16), the formula (B1a-18), the formula (B1a-19), and the formula (B1a-22) to the formula (B1a-38) are preferred.

[0239] Z1 + Examples of the organic cation of 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 the formula (b2-1) to the formula (b2-4) (hereinafter, may be referred to as "cation (b2-1)" etc. according to the formula number) are included. In formulas (b2-1) to (b2-4) of TIFF0007691875000136, R b4 ~R b6 each independently represents a linear 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 linear 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; 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 -CH 2 - 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 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 R b8 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 -CH 2- may be replaced by -O-, -S- or -CO-. R b11 represents a hydrogen atom, a chain 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 chain 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 chain hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms. R b11 and R b12 and may be bonded to each other to form a ring including -CH-CO- to which they are bonded, and -CH 2 - may be replaced by -O-, -S- or -CO-. R b13 ~R b18 each independently represents a halogen atom, a hydroxy group, an 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, when p2 is 2 or more, the plurality of R b14 are the same or different, when q2 is 2 or more, the plurality of R b15 are the same or different, when r2 is 2 or more, the plurality of R b16 are the same or different, when s2 is 2 or more, the plurality of R b17 are the same or different, when t2 is 2 or more, the plurality of R 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 having 1 to 12 carbon atoms. 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, cyclodecyl group, etc. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups, etc. TIFF0007691875000137.tif10159 In particular, R b9 ~R b12 The alicyclic hydrocarbon group of is preferably having 3 to 18 carbon atoms, more preferably having 4 to 12 carbon atoms. 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, isobornyl group, etc. 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 having a fluorine atom, and examples thereof include fluoromethyl group, difluoromethyl group, trifluoromethyl group, perfluorobutyl, etc. The number of carbon atoms of the alkyl fluoride group is preferably 1 to 9, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, biphenyl group, naphthyl group, and 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 tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) and an aromatic hydrocarbon group having an alicyclic hydrocarbon group with 3 to 18 carbon atoms (such as p-cyclohexylphenyl group, p-adamantylphenyl group, etc.). 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 p-methoxyphenyl group and the like. Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, and naphthylethyl group. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, and dodecyloxy group. Examples of the alkylcarbonyl group include acetyl group, propionyl group, and butyryl group. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom. Examples of the alkylcarbonyloxy group include methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyloxy group, and 2-ethylhexylcarbonyloxy group. R b4 and R b5The ring formed by the combination of them together with the sulfur atom to which they are attached 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 rings to 12-membered rings, preferably 3-membered rings to 7-membered rings, and examples thereof include the following rings. * represents a bonding position. TIFF0007691875000138.tif23144R b9 and R b10 The ring formed by the combination of them together may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. Examples of this ring include 3-membered rings to 12-membered rings, preferably 3-membered rings to 7-membered rings. Examples thereof include thiolan-1-ium ring (tetrahydrothiophenium ring), thian-1-ium ring, 1,4-oxathian-4-ium ring and the like. R b11 and R b12 The ring formed by the combination of them together may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. Examples of this ring include 3-membered rings to 12-membered rings, preferably 3-membered rings to 7-membered rings. Examples thereof include oxocycloheptane ring, oxocyclohexane ring, oxonorbornane ring, oxoadamantane ring and the like.

[0240] Among cations (b2-1) to (b2-4), preferably, it is cation (b2-1). Examples of cation (b2-1) include the following cations. TIFF0007691875000139.tif79158

[0241] TIFF0007691875000140.tif109165

[0242] Examples of cation (b2-2) include the following cations and the like. TIFF0007691875000141.tif18150

[0243] Examples of the cation (b2-3) include the following cations and the like. TIFF0007691875000142.tif25122

[0244] Examples of the cation (b2-4) include the following cations and the like. TIFF0007691875000143.tif127166

[0245] The acid generator (B) is a combination of the above-mentioned anion and the above-mentioned organic cation, and these can be arbitrarily combined. As the acid generator (B), preferably, a combination of 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) and the cation (b2-1), the cation (b2-3) or the cation (b2-4) is mentioned.

[0246] As the acid generator (B), preferably, those represented by Formula (B1-1) to Formula (B1-56) are mentioned. Among them, those containing an arylsulfonium cation are preferable, and those represented by Formula (B1-1) to Formula (B1-3), Formula (B1-5) to Formula (B1-7), Formula (B1-11) to Formula (B1-14), Formula (B1-20) to Formula (B1-26), Formula (B1-29), Formula (B1-31) to Formula (B1-56) are particularly preferable. TIFF0007691875000144.tif98162

[0247] TIFF0007691875000145.tif119163

[0248] TIFF0007691875000146.tif127158

[0249] TIFF0007691875000147.tif98161

[0250] TIFF0007691875000148.tif134130

[0251] TIFF0007691875000149.tif92158

[0252] 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 1 part by mass or more and 40 parts by mass or less, 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).

[0253] <Solvent (E)> The content of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less, 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 of the solvent (E) can be measured by known analytical 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.

[0254] <Quencher (C)> The quencher (C) includes a basic nitrogen-containing organic compound or a salt that generates an acid having a lower acidity than the acid generated from 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 compounds 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.

[0255] 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. The salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is preferably 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 the weak acid inner salt (D). TIFF0007691875000150.tif94164

[0256] Examples of the weak acid inner salt (D) include the following salts. TIFF0007691875000151.tif72165

[0257] 〈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.

[0258] 〈Preparation of Resist Composition〉 The resist composition of the present invention can be prepared by mixing a resin containing a carboxylate represented by formula (I) or a structural unit represented by formula (I-1), optionally, resin (A), acid generator (B), a resin other than resin (A), solvent (E), quencher (C), and other components (F), etc. 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.

[0259] 〈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 and organic substrates having a resist film or the like formed on the surface. Before applying the resist composition, the substrate may be cleaned, or an antireflection film or the like may be formed on the substrate. By drying the applied 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-baking), 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 a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F 2 excimer laser (wavelength 157 nm), those that convert laser light from a solid laser light source (such as a YAG or semiconductor laser) into harmonic laser light in the far ultraviolet region or vacuum ultraviolet region and emit it, those that irradiate electron beams, those that irradiate extreme ultraviolet light (EUV), etc. can be used. In this specification, irradiating these radiations may be collectively referred to as "exposure". During exposure, exposure is usually 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. Chemical treatment (silylation) may be performed to adjust the hydrophilicity or hydrophobicity of the resin on the surface side of the composition after heating. Also, before development, the steps of coating, drying, exposing, and heating the resist composition may be repeated on the exposed composition layer. 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, (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline), etc. may 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-based developer") is used as the developer. Examples of the organic solvent contained in the organic-based 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; aromatic hydrocarbon solvents such as anisole, etc. In the organic-based 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-based developer, a developer containing butyl acetate and / or 2-heptanone is preferable. In the organic-based 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-based developer may contain a surfactant. Also, the organic-based developer may contain a trace amount of water. During development, development may be stopped by substituting with a solvent of a different type from the organic-based 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.

[0260] <Use> 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 electron beam (EB) exposure or a resist composition for EUV exposure, and is useful for semiconductor microfabrication.

Examples

[0261] The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing content or usage amount 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 1100 type, MASS is Agilent LC / MSD type). In the following examples, the value of this molecular ion peak is indicated by “MASS”.

[0262] Example 1: Synthesis of the salt represented by formula (I-2) 20 parts of the compound represented by formula (I-2-a), 2.28 parts of the compound represented by formula (I-2-c), 100 parts of ethyl acetate and 15 parts of tetrahydrofuran were mixed and stirred at 23 °C for 30 minutes. To the resulting mixed solution, 6.55 parts of the compound represented by formula (I-2-b) was added and stirred at 23 °C for 18 hours. To the resulting reaction mass, 20 parts of n-heptane and 70 parts of ion-exchanged water were added and stirred at 23 °C for 30 minutes, and then separated to extract the organic layer. 60 parts of ion-exchanged water was added to the recovered organic layer and stirred at 23 °C for 30 minutes, and then separated to extract the organic layer. This water washing operation was repeated 4 times. The obtained organic layer was concentrated, and the concentrated mass was fractionated by a column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain 7.48 parts of the compound represented by formula (I-2-d). 0.95 part of the compound represented by formula (I-2-d) and 10 parts of tetrahydrofuran were mixed and stirred at 23 °C for 30 minutes, then cooled to 5 °C, and 0.14 part of sodium hydride was added. To the resulting mixture, 1.81 parts of the salt represented by formula (I-2-e) was added and stirred at 5 °C for 3 hours. To the resulting mixture, 6.30 parts of 1N hydrochloric acid was added, then the temperature was raised to 23 °C and stirred at 23 °C for 6 hours. To the resulting mixture, 30 parts of chloroform and 15 parts of ion-exchanged water were added and stirred at 23 °C for 30 minutes, and then separated to extract the organic layer. After concentrating the obtained organic layer, 1 part of acetonitrile and 30 parts of tert-butyl methyl ether were added to the concentrated residue, stirred at 23 °C for 30 minutes, then the supernatant was removed and concentrated to obtain 1.52 parts of the salt represented by formula (I-2-f). After adding 0.20 part of the compound represented by TIFF0007691875000154.tif62128 formula (I-2-g) and 20 parts of chloroform, the mixture was stirred at 23 °C for 30 minutes. To the resulting mixture, 0.38 part of carbonyldiimidazole was added, and the mixture was stirred at 50 °C for 2 hours. To the resulting mixture, 0.95 part of the salt represented by formula (I-2-f) was mixed, and after stirring at 50 °C for 2 hours, it was cooled to 23 °C. To the resulting mixture, 20 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added, and after stirring at 23 °C for 30 minutes, liquid separation was performed to take out the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added, and after stirring at 23 °C for 30 minutes, liquid separation was performed to take out the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.86 part of the salt represented by formula (I-2-h) was obtained. 0.59 part of the salt represented by TIFF0007691875000155.tif66136 formula (I-2-h), 0.37 part of the salt represented by formula (I-2-i), and 20 parts of chloroform were mixed and stirred at 23 °C for 12 hours. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution was added, and after stirring at 23 °C for 30 minutes, liquid separation was performed to take out the organic layer. To the obtained organic layer, 10 parts of ion-exchanged water was added, and after stirring at 23 °C for 30 minutes, liquid separation was performed to take out the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.71 part of the salt represented by formula (I-2) was obtained. MASS(ESI(+)Spectrum):M + 437.1 MASS(ESI(-)Spectrum):M - 193.1

[0263] Example 2: Synthesis of the salt represented by formula (I-4) 0.59 part of the salt represented by TIFF0007691875000156.tif66140 formula (I-2-h), 0.55 part of the salt represented by formula (I-4-i) and 20 parts of chloroform were mixed and stirred at 23 °C for 12 hours. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution was added and stirred at 23 °C for 30 minutes, and then the layers were separated to extract the organic layer. To the obtained organic layer, 10 parts of ion-exchanged water was added and stirred at 23 °C for 30 minutes, and then the layers were separated to extract the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.88 part of the salt represented by formula (I-4) was obtained. MASS(ESI(+)Spectrum):M + 437.1 MASS(ESI(-)Spectrum):M - 337.1

[0264] Example 3: Synthesis of the salt represented by formula (I-3044) 6.57 parts of the compound represented by TIFF0007691875000157.tif37139 formula (I-3044-a), 0.23 part of the compound represented by formula (I-2-c), 30 parts of ethyl acetate and 15 parts of tetrahydrofuran were mixed and stirred at 23 °C for 30 minutes. To the resulting mixed solution, 0.66 part of the compound represented by formula (I-2-b) was added and stirred at 23 °C for 18 hours. To the obtained reaction mass, 100 parts of n-heptane and 20 parts of ion-exchanged water were added and stirred at 23 °C for 30 minutes, and then the layers were separated to extract the organic layer. To the recovered organic layer, 20 parts of ion-exchanged water was added and stirred at 23 °C for 30 minutes, and then the layers were separated to extract the organic layer. This water washing operation was repeated 4 times. The obtained organic layer was concentrated, and the concentrated mass was fractionated by column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain 6.28 parts of the compound represented by formula (I-3044-d). 2.26 parts of the compound represented by TIFF0007691875000158.tif63167 (I-3044-d) and 10 parts of tetrahydrofuran were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C, and 0.14 part of sodium hydride was added. To the resulting mixture, 1.81 parts of the salt represented by the formula (I-2-e) was added, and the mixture was stirred at 5°C for 3 hours. To the resulting mixture, 6.30 parts of 1N hydrochloric acid was added, then the temperature was raised to 23°C, and the mixture was stirred at 23°C for 6 hours. To the resulting mixture, 30 parts of chloroform and 15 parts of ion-exchanged water were added, and the mixture was stirred at 23°C for 30 minutes, then separated to obtain the organic layer. After concentrating the obtained organic layer, 1 part of acetonitrile and 30 parts of tert-butyl methyl ether were added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes, then the supernatant was removed and concentrated to obtain 2.66 parts of the salt represented by the formula (I-3044-f). 0.20 part of the compound represented by TIFF0007691875000159.tif57135 (I-2-g) and 20 parts of chloroform were added, and the mixture was stirred at 23°C for 30 minutes. To the resulting mixture, 0.38 part of carbonyldiimidazole was added, and the mixture was stirred at 50°C for 2 hours. To the resulting mixture, 1.54 parts of the salt represented by the formula (I-3044-f) was mixed, and the mixture was stirred at 50°C for 2 hours, then cooled to 23°C. To the resulting mixture, 20 parts of chloroform and 20 parts of 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23°C for 30 minutes, 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, then separated to obtain the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.66 parts of the salt represented by the formula (I-3044-h) was obtained. 0.90 part of the salt represented by TIFF0007691875000160 (I-3044-h), 0.55 part of the salt represented by formula (I-4-i), and 20 parts of chloroform were mixed and stirred at 23 °C for 12 hours. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution was added and stirred at 23 °C for 30 minutes, and then liquid separation was performed to take out the organic layer. To the obtained organic layer, 10 parts of ion-exchanged water was added and stirred at 23 °C for 30 minutes, and then liquid separation was performed to take out the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.14 parts of the salt represented by formula (I-3044) was obtained. MASS(ESI(+)Spectrum):M + 688.9 MASS(ESI(-)Spectrum):M - 337.1

[0265] Example 4: Synthesis of the salt represented by formula (I-1999) 0.95 part of the compound represented by TIFF0007691875000161 (I-2-d) and 10 parts of tetrahydrofuran were mixed and stirred at 23 °C for 30 minutes, then cooled to 5 °C, and 0.14 part of sodium hydride was added. To the resulting mixture, 2.59 parts of the salt represented by formula (I-1999-e) was added and stirred at 5 °C for 3 hours. To the obtained mixture, 6.30 parts of 1N hydrochloric acid was added, then the temperature was raised to 23 °C and stirred at 23 °C for 6 hours. To the obtained mixture, 30 parts of chloroform and 15 parts of ion-exchanged water were added and stirred at 23 °C for 30 minutes, and then liquid separation was performed to take out the organic layer. After concentrating the obtained organic layer, to the concentrated residue, 1 part of acetonitrile and 30 parts of tert-butyl methyl ether were added and stirred at 23 °C for 30 minutes, then the supernatant was removed and concentrated to obtain 2.72 parts of the salt represented by formula (I-1999-f). After adding 0.20 part of the compound represented by TIFF0007691875000162.tif62135 (I-2-g) and 20 parts of chloroform, the mixture was stirred at 23 °C for 30 minutes. To the resulting mixture, 0.38 part of carbonyldiimidazole was added, and the mixture was stirred at 50 °C for 2 hours. To the resulting mixture, 1.27 parts of the salt represented by formula (I-1999-f) was mixed, and after stirring at 50 °C for 2 hours, it was cooled to 23 °C. To the resulting mixture, 20 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution 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, 1.36 parts of the salt represented by formula (I-1999-h) was obtained. 0.76 part of the salt represented by TIFF0007691875000163.tif68147 (I-1999-h), 0.55 part of the salt represented by formula (I-4-i) and 20 parts of chloroform were mixed and stirred at 23 °C for 12 hours. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution was 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, 10 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, 1.03 parts of the salt represented by formula (I-1999) was obtained. MASS(ESI(+)Spectrum):M + 573.1 MASS(ESI(-)Spectrum):M - 337.1

[0266] Example 5: Synthesis of the salt represented by formula (I-859) After adding 0.48 part of the compound represented by formula (I-859-g) and 20 parts of chloroform, the mixture was stirred at 23 °C for 30 minutes. To the resulting mixture, 0.38 part of carbonyldiimidazole was added, and the mixture was stirred at 50 °C for 2 hours. To the resulting mixture, 0.95 part of the salt represented by formula (I-2-f) was added, and the mixture was stirred at 50 °C for 2 hours and then cooled to 23 °C. To the resulting mixture, 20 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23 °C for 30 minutes, followed by liquid separation to take out 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, followed by liquid separation to take out the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.21 parts of the salt represented by formula (I-859-h) was obtained. 0.74 part of the salt represented by formula (I-859-h), 0.55 part of the salt represented by formula (I-4-i) and 20 parts of chloroform were mixed and stirred at 23 °C for 12 hours. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 °C for 30 minutes, followed by liquid separation to take out the organic layer. To the obtained organic layer, 10 parts of ion-exchanged water was added, and the mixture was stirred at 23 °C for 30 minutes, followed by liquid separation to take out the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.02 parts of the salt represented by formula (I-859) was obtained. MASS(ESI(+)Spectrum):M + 557.1 MASS(ESI(-)Spectrum):M - 337.1

[0267] 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. TIFF0007691875000166.tif115163

[0268] Example 6 [Synthesis of Resin A1] As monomers, acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6) and monomer (I-2) were used, and they were mixed so that the molar ratio [acetoxystyrene: monomer (a1-1-3): monomer (a1-2-6): monomer (I-2)] was 38:24:35:3. Further, 1.5 times the mass of methyl isobutyl ketone with respect to the total mass of all monomers was mixed into this monomer mixture. To the obtained mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% with respect to the total number of moles of all monomers, and polymerization was carried out by heating this at 75 °C for about 5 hours. Thereafter, an aqueous solution of 25% tetramethylammonium hydroxide was added to the polymerization reaction solution, and after stirring for 12 hours, liquid separation was carried out. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was filtered and recovered, whereby resin A1 (copolymer) having a weight average molecular weight of about 5.2×10 3 was obtained at a yield of 81%. This resin A1 has the following structural units. TIFF0007691875000167.tif53141

[0269] Example 7 [Synthesis of Resin A2] As monomers, acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6) and monomer (I-4) were used, and they were mixed so that the molar ratio [acetoxystyrene: monomer (a1-1-3): monomer (a1-2-6): monomer (I-4)] was 38:24:35:3. Further, 1.5 times the mass of methyl isobutyl ketone with respect to the total mass of all monomers was mixed into this monomer mixture. To the obtained mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% with respect to the total number of moles of all monomers, and polymerization was carried out by heating this at 75 °C for about 5 hours. Thereafter, an aqueous solution of 25% tetramethylammonium hydroxide was added to the polymerization reaction solution, and after stirring for 12 hours, liquid separation was carried out. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was filtered and recovered, whereby resin A2 (copolymer) having a weight average molecular weight of about 5.3×10 3 was obtained at a yield of 78%. This resin A2 has the following structural units. TIFF0007691875000168.tif54148

[0270] Example 8 [Synthesis of Resin A3] As monomers, acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6) and monomer (I-3044) were used, and their molar ratio [acetoxystyrene: monomer (a1-1-3): monomer (a1-2-6): monomer (I-3044)] was mixed so as to be 38:24:35:3. Further, 1.5 times the mass of methyl isobutyl ketone with respect to the total mass of all monomers was mixed into this monomer mixture. To the obtained mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% with respect to the total number of moles of all monomers, and polymerization was carried out by heating this at 75 °C for about 5 hours. Thereafter, an aqueous solution of 25% tetramethylammonium hydroxide was added to the polymerization reaction solution, 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 with a weight average molecular weight of about 5.1×10 3 and resin A3 (copolymer) was obtained in a yield of 66%. This resin A3 has the following structural units. TIFF0007691875000169.tif54149

[0271] Example 9 [Synthesis of Resin A4] As monomers, acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6) and monomer (I-1999) were used, and they were mixed so that the molar ratio [acetoxystyrene: monomer (a1-1-3): monomer (a1-2-6): monomer (I-1999)] was 38:24:35:3. Further, 1.5 times the mass of methyl isobutyl ketone with respect to the total mass of all monomers was mixed into this monomer mixture. To the obtained mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% with respect to the total number of moles of all monomers, and polymerization was carried out by heating this at 75 °C for about 5 hours. Thereafter, an aqueous solution of 25% tetramethylammonium hydroxide was added to the polymerization reaction solution, and after stirring for 12 hours, liquid separation was performed. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was filtered and recovered, whereby a resin A4 (copolymer) having a weight average molecular weight of about 5.4×10 3 was obtained at a yield of 72%. This resin A4 has the following structural units. TIFF0007691875000170.tif55149

[0272] Example 10 [Synthesis of Resin A5] As monomers, acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6) and monomer (I-859) were used, and they were mixed so that the molar ratio [acetoxystyrene: monomer (a1-1-3): monomer (a1-2-6): monomer (I-859)] was 38:24:35:3. Further, 1.5 times the mass of methyl isobutyl ketone with respect to the total mass of all monomers was mixed into this monomer mixture. To the obtained mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% with respect to the total number of moles of all monomers, and polymerization was carried out by heating this at 75 °C for about 5 hours. Thereafter, an aqueous solution of 25% tetramethylammonium hydroxide was added to the polymerization reaction solution, and after stirring for 12 hours, liquid separation was performed. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was filtered and recovered, whereby a resin having a weight average molecular weight of about 5.5×10 3Resin A5 (copolymer) was obtained in a yield of 80%. This resin A5 has the following structural units. TIFF0007691875000171.tif74149

[0273] Synthesis Example 1 [Synthesis of Resin AX1] As monomers, acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6), and monomer (IX-1) were used, and they were mixed so that the molar ratio [acetoxystyrene: monomer (a1-1-3): monomer (a1-2-6): monomer (IX-1)] was 38:24:35:3. Further, 1.5 mass times of methyl isobutyl ketone was mixed with this monomer mixture based on the total mass of all monomers. To the obtained 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 75 °C for about 5 hours. Then, an aqueous solution of 25% tetramethylammonium hydroxide was added to the polymerization reaction solution, and after stirring for 12 hours, liquid separation was carried out. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was filtered and recovered, whereby a resin AX1 (copolymer) having a weight average molecular weight of about 5.4×10 3 was obtained in a yield of 81%. This resin AX1 has the following structural units. TIFF0007691875000172.tif38139

[0274] Synthesis Example 2 [Synthesis of Resin AA1] As monomers, monomer (a1-4-2), monomer (a1-1-3) and monomer (a1-2-6) were used and mixed so that the 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 with respect to the total mass of all monomers was mixed into this monomer mixture. To the resulting mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% with respect to the total number of moles of all monomers, and polymerization was carried out by heating this at 85 °C for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, stirred for 6 hours, and then liquid-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 AA1 (copolymer) having the following was obtained in a yield of 78%. TIFF0007691875000173.tif29131

[0275] Synthesis Example 3 [Synthesis of Resin AA2] As monomers, monomer (a1-4-2) and monomer (a1-2-6) were used and mixed so that the molar ratio [monomer (a1-4-2): monomer (a1-2-6)] was 38:62. Further, 1.5 times the mass of methyl isobutyl ketone with respect to the total mass of all monomers was mixed into this monomer mixture. To the resulting mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% with respect to the total number of moles of all monomers, and polymerization was carried out by heating this at 85 °C for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, stirred for 6 hours, and then liquid-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 AA2 (copolymer) having the following was obtained in a yield of 89%. TIFF0007691875000174.tif2891

[0276] <Preparation of Resist Composition> As shown in Table 2, each of the following components was mixed, and the resulting mixture was filtered through a fluororesin filter with a pore size of 0.2 μm to prepare a resist composition.

Table 2

[0277] <Resin> A1 to A5, AA1, AA2, AX1: Resin A1 to Resin A5, Resin AA1, Resin AA2, Resin AX1 <Acid Generator> B1-25: Salt represented by formula (B1-25); synthesized by the method described in JP-A-2011-126869 TIFF0007691875000176.tif2667<Carboxylate (I)> I-2: Salt represented by formula (I-2) I-4: Salt represented by formula (I-4) I-859: Salt represented by formula (I-859) I-1999: Salt represented by formula (I-1999) I-3044: Salt represented by formula (I-3044) <Quencher (C)> C1: Synthesized by the method described in JP-A-2011-39502 TIFF0007691875000177.tif3647IX-1: TIFF0007691875000178.tif3449<Solvent> Propylene Glycol Monomethyl Ether Acetate 400 parts Propylene Glycol Monomethyl Ether 100 parts γ-Butyrolactone 5 parts

[0278] (Electron Beam Exposure Evaluation of Resist Composition) A 6-inch silicon wafer was treated with hexamethyldisilazane at 90 °C for 60 seconds on a direct hot plate. A resist composition was spin-coated onto this silicon wafer so that the film thickness of the composition layer was 0.04 μm. Then, it was prebaked for 60 seconds at the temperature shown in the "PB" column of Table 2 on a direct hot plate to form a composition layer. Using an electron beam lithography machine ["HL-800D 50keV" manufactured by Hitachi, Ltd.], a line and space pattern was directly drawn on the composition layer formed on the wafer by gradually changing the exposure dose. After exposure, post-exposure baking was performed for 60 seconds at the temperature shown in the "PEB" column of Table 2 on a hot plate, and further 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 dose at which the line width and space width of the 60-nm line and space pattern became 1:1 was defined as the effective sensitivity.

[0279] 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

Industrial Applicability

[0280] 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 semiconductor microfabrication and is extremely useful industrially.

Claims

1. A carboxylate represented by formula (I). [In formula (I), R １ , R ２ and R ３ each independently represents a group represented by formula (4a). R ４ 、R ５ 、R ６ 、R ７ 、R ８ and R ９ each independently represents a halogen atom, a hydroxy group, an alkyl fluoride group having 1 to 12 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms, the hydrocarbon group may have a substituent, and -CH 2 - in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO ２ -. X １ , X ２ and X ３ 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 within multiple parentheses may be the same or different from each other. m2 represents any integer from 0 to 4, and when m2 is 2 or more, the groups within multiple parentheses may be the same or different from each other. m3 represents any integer from 0 to 4, and when m3 is 2 or more, the groups within multiple parentheses may be the same 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, and when m5 is 2 or more, the plurality of Rs ５ may be the same as or different from each other. m6 represents any integer from 0 to 4, and when m6 is 2 or more, the plurality of Rs ６ may be the same as or different from each other. m7 represents any integer from 0 to 5, 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 4, and when m8 is 2 or more, the plurality of Rs ８ may be the same as or different from each other. m9 represents any integer from 0 to 4, and when m9 is 2 or more, the plurality of Rs ９ may be the same as or different from each other. However, 1 ≦ m1 + m7 ≦ 5, 0 ≦ m2 + m8 ≦ 4, and 0 ≦ m3 + m9 ≦ 4. X ４ represents a single bond, -CH 2 -, -O-, -S-, -CO-, -SO- or -SO ２ -. X ０ represents an alicyclic hydrocarbon group having 3 to 36 carbon atoms which may have a fluorine atom or a hydroxy group (wherein -CH2- contained in the alicyclic 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 halogen atom, a hydroxy group or a perfluoroalkyl group having 1 to 4 carbon atoms. [In formula (4a), R １０ represents a hydrogen atom or a methyl group. X １０ represents a group represented by any one of formulas (X1-1) to (X1-7). (In formula (X １ -1) to formula (X １ -7), *, ** are binding sites, and ** represents the binding site with L 1０ (which represents the binding site with L.) L １０ represents a hydrocarbon group having 1 to 36 carbon atoms which may have a single bond or a substituent, and -CH 2 - in the hydrocarbon group may be replaced by -O-, -S-, -SO ２ - or -CO-. *10 represents the bonding site with the benzene ring.]

2. X １ , X ２ and X ３ The carboxylate according to claim 1, wherein X, X and X are oxygen atoms.

3. X １０ is a group represented by any one of formula (X １ -1), formula (X １ -4) and formula (X １ -5). The carboxylate according to claim 1 or 2.

4. L １０ is a single bond or an alkanediyl group having 1 to 4 carbon atoms (however, -CH 2 - contained in the alkanediyl group may be replaced by -O- or -CO-). The carboxylate according to any one of claims 1 to 3.

5. m1 is 1 or 2, m4 is 1 or 2, and R ４ is a halogen atom, and the carboxylate according to any one of claims 1 to 4.

6. m2 and m3 are 0, m8 and m9 are 1, R ８ and R ９ The carboxylate salt according to any one of claims 1 to 5, wherein each of them is independently a halogen atom or a C1-C5 perfluoroalkyl group.

7. A carboxylic acid generator containing the carboxylate according to any one of Claims 1 to 6.

8. A resin containing a structural unit derived from the carboxylate according to any one of Claims 1 to 6.

9. The resin according to Claim 8, further containing a structural unit having an acid-labile group.

10. A resist composition containing the carboxylic acid generator according to Claim 7, an acid generator other than the carboxylic acid generator, and a resin containing a structural unit having an acid-labile group.

11. A resist composition containing the resin according to Claim 9 and an acid generator.

12. The resist composition according to Claim 10 or 11, wherein the resin containing a structural unit 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 any integer from 0 to 14. n1 represents any integer from 0 to 10. n1’ represents any integer from 0 to 3.]

13. The resist composition according to any one of Claims 10 to 12, wherein the resin containing a structural unit 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 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.]

14. (1) A step of applying the resist composition according to any one of Claims 10 to 13 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, comprising the steps of.

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