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

Abstract

To provide carboxylate, a carboxylic acid generator including the carboxylate and a resist composition including the generator from which a resist pattern having an excellent mask error factor (MEF) can be produced.SOLUTION: Provided is carboxylate expressed by and synthesized as in a formula (I-2), for instance.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Patent Document 1 describes a resist composition containing a carboxylate represented by the following formula as a carboxylic acid generator. TIFF0007704551000001.tif2641 Patent Document 2 describes a resist composition containing a salt represented by the following formula as an acid generator. TIFF0007704551000002.tif2684 Patent Document 3 describes a resist composition containing a salt represented by the following formula as an acid generator. TIFF0007704551000003.tif2887

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present invention provides a carboxylate that forms a resist pattern with a better mask error factor (MEF) than a resist pattern formed by a resist composition containing the above salt.

Means for Solving the Problems

[0005] The present invention includes the following inventions. [1] The carboxylate salt represented by formula (I). TIFF0007704551000004.tif97117[In formula (I), R 1 、R 2 and R 3 each independently represent -O-R 10 、-O-CO-R 10 、-O-CO-O-R 10 、-O-L 1 -CO-O-R 10 . L 1 represents an alkanediyl group having 1 to 6 carbon atoms. R 4 、R 5 、R 6 、R 7 、R 8 and R 9 each independently represent a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 18 carbon atoms, and the hydrocarbon group may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -CO-, -S- or -SO2-. R 10 represents an alicyclic hydrocarbon group having one or more -OR 11 groups. When there are a plurality of R11, they may be the same as or different from each other. R 11 represents a hydrogen atom or an acid-labile group. X 1 、X 2 and X 3 each independently represent an oxygen atom or a sulfur atom. m1 represents an integer of any one of 1 to 5. When m1 is 2 or more, the groups in a plurality of parentheses may be the same as or different from each other. m2 represents an integer of any one of 0 to 5. When m2 is 2 or more, the groups in a plurality of parentheses may be the same as or different from each other. m3 represents an integer of any one of 0 to 5. When m3 is 2 or more, the groups in a plurality of parentheses may be the same as or different from each other. When m2 or m3 is 1 or more and there are a plurality of R 10 , they may be the same as or different from each other. m4 represents an integer from 0 to 4. When m4 is 2 or more, the plurality of Rs 4 may be the same as or different from each other. m5 represents an integer from 0 to 4. When m5 is 2 or more, the plurality of Rs 5 may be the same as or different from each other. m6 represents an integer from 0 to 4. When m6 is 2 or more, the plurality of Rs 6 may be the same as or different from each other. m7 represents an integer from 0 to 4. When m7 is 2 or more, the plurality of Rs 7 may be the same as or different from each other. m8 represents an integer from 0 to 5. When m8 is 2 or more, the plurality of Rs 8 may be the same as or different from each other. m9 represents an integer from 0 to 5. 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 ≦ 5, and 0 ≦ m3 + m9 ≦ 5. X 0 represents a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. [2] X 1 , X 2 and X 3 are oxygen atoms, and the carboxylate salt according to [1]. [3] R 10 is an adamantyl group having an -OR 11 group (R 11 represents a hydrogen atom or an acid-labile group.), and the carboxylate salt according to [1] or [2]. [4] The acid-labile group of R 11 is a group represented by the formula (1a) or a group represented by the formula (2a), and the carboxylate salt according to any one of [1] to [3]. TIFF0007704551000005.tif2267 [In the formula (1a), R aa1 , R aa2 and R aa3each independently represents an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 8 carbon atoms which may have a substituent, an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or R aa1 and R aa2 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. naa represents 0 or 1. * represents a bond.] TIFF0007704551000006.tif2358[In formula (2a), R aa1’ and R aa2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R aa3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R aa2’ and R aa3’ are bonded to each other to form a heterocyclic group having 3 to 20 carbon atoms together with the -C-X a -, and the -CH2- contained in the hydrocarbon group and the heterocyclic group may be replaced by -O- or -S-. X a represents an oxygen atom or a sulfur atom. * represents a bond.] [5]X 0 is an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (however, the -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent, which is the carboxylate according to any one of [1] to [4]. [6]X 0 is an alicyclic hydrocarbon group having 3 to 36 carbon atoms which may have a fluorine atom or a hydroxy group (the -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or an aromatic hydrocarbon group having 6 carbon atoms which may have a halogen atom, a hydroxy group or a perfluoroalkyl group having 1 to 4 carbon atoms, which is the carboxylate according to any one of [1] to [5]. [7]X0 The carboxylate salt according to [5], which is a group represented by formula (aa). TIFF0007704551000007.tif2636[In formula (aa), X a and X b each independently represents -O- or -S-. X 1a represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. X 2a represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. * represents the bonding position with the carbon atom of -COO - .] [8]X 0 is the carboxylate salt according to [5], which is an aromatic hydrocarbon group having 6 to 36 carbon atoms having a halogen atom, a hydroxy group or a perfluoroalkyl group having 1 to 4 carbon atoms. [9]X 0 is the carboxylate salt according to [5], which is a group represented by formula (bb). TIFF0007704551000008.tif2351[In formula (bb), L A represents an alkanediyl group having 1 to 6 carbon atoms which may have a fluorine atom, or an aromatic hydrocarbon group having 6 carbon atoms which may have a halogen atom or a perfluoroalkyl group having 1 to 4 carbon atoms. L B represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, and -CH2- contained in the alkanediyl group may be replaced by -O-, -S-, -CO- or -SO2-. R A represents a hydrocarbon group having 1 to 36 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. * represents -COO -represents the bonding position with the carbon atom.]

[10] A carboxylic acid generator containing the carboxylate salt described in any one of [1] to [9].

[11] A resist composition containing the carboxylic acid generator described in

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

[12] The resist composition according to

[11] , wherein the resin having an acid-labile group contains at least one selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2). TIFF0007704551000009.tif46102 [In formula (a1-1) and formula (a1-2), L a1 and L a2 each independently represents -O- or *-O-(CH2) k1 -CO-O-, k1 represents an integer of any one of 1 to 7, and * represents the bonding position with -CO-. R a4 and R a5 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. m1 represents an integer of any one of 0 to 14. n1 represents an integer of any one of 0 to 10. n1' represents an integer of any one of 0 to 3.]

[13] Further, the resist composition according to

[11] or

[12] , containing a resin containing a structural unit having a fluorine atom.

[14] (1) A step of applying the resist composition according to any one of

[11] 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 A method for manufacturing a resist pattern, comprising the step of developing the composition layer after heating.

Advantages of the Invention

[0006] By using the resist composition containing the carboxylate of the present invention, a resist pattern can be manufactured with a good mask error factor (MEF).

Embodiments for Carrying Out the Invention

[0007] As used herein, the term “(meth)acrylic monomer” means at least one selected from the group consisting of monomers having the structure of “CH2=CH-CO-” and monomers having the structure of “CH2=C(CH3)-CO-”. Similarly, “(meth)acrylate” and “(meth)acrylic acid” mean “at least one selected from the group consisting of acrylate and methacrylate” and “at least one selected from the group consisting of acrylic acid and methacrylic acid”, respectively. When structural units having “CH2=C(CH3)-CO-” or “CH2=CH-CO-” are exemplified, structural units having both groups are similarly exemplified. Also, among the groups described in this specification, those that can take both a linear structure and a branched structure may be either. When -CH2- contained in a hydrocarbon group or the like is replaced by -O-, -S-, -CO- or -SO2-, the same examples apply to each group. The term “combined group” means a group formed by bonding two or more of the exemplified groups, and the valences of these groups may be appropriately changed depending on the bonding form. The terms “derived from” or “induced from” refer to the fact that the polymerizable C=C bond contained in the molecule becomes a -C-C- group by polymerization. When stereoisomers exist, all stereoisomers are included. As used herein, the “solid content of the resist composition” means the total of the components excluding the solvent (E) described below from the total amount of the resist composition.

[0008]

Salt Represented by Formula (I)

[0009] In formula (I), R 1 , R 2 and R 3 The alkane diyl group in L 1 contained in may include linear alkane diyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group; and branched alkane diyl 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 and the like. L 1 is preferably an alkane diyl group having 1 to 3 carbon atoms, and more preferably a methylene group. R 1 , R 2 and R 3 The alicyclic hydrocarbon group of R 10 contained in 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 and the like. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group and the like. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 16, and still more preferably 3 to 12. Specifically, examples of the alicyclic hydrocarbon group include the groups represented below and the like. The bonding site can be at any position. TIFF0007704551000011.tif41165R 10 The alicyclic hydrocarbon group is preferably an adamantyl group, among others.

[0010] R 11 The acid-labile group of R means a group that, when contacted with an acid (e.g., trifluoromethanesulfonic acid), eliminates the group represented by R 11 to form a hydroxy group. As the acid-labile group, a group represented by formula (1a) (hereinafter, sometimes referred to as "acid-labile group (1a)") and a group represented by formula (2a) (hereinafter, sometimes referred to as "acid-labile group (2a)") are preferable. TIFF0007704551000012.tif2466[In formula (1a), R aa1 , R aa2 and R aa3 each independently represent an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 2 to 8 carbon atoms, an optionally substituted alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or R aa1 and R aa2 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. naa represents 0 or 1. * represents a bond.] TIFF0007704551000013.tif2163[In formula (2a), R aa1’ and R aa2’ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R aa3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R aa2’ and R aa3’ are bonded to each other to form a heterocyclic group having 3 to 20 carbon atoms together with the -C-X a - to which they are bonded, and the -CH2- contained in the hydrocarbon group and the heterocyclic group may be replaced by -O- or -S-. X a represents an oxygen atom or a sulfur atom. * represents a bond.]

[0011] R aa1 , R aa2 and R aa3 Examples of the alkyl group of R include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group. aa1 , R aa2 and R aa3 The alkyl group preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms. R aa1 , R aa2 and R aa3 Examples of the alkenyl group include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octynyl, isooctynyl, and nonenyl groups. R aa1 , R aa2 and R aa3 The alicyclic hydrocarbon group of may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl, adamantyl, and norbornyl groups, and the following groups (* represents a bond). R aa1 , R aa2 and R aa3 The alicyclic hydrocarbon group preferably has 3 to 16 carbon atoms, and more preferably has 3 to 12 carbon atoms. TIFF0007704551000014.tif9159R aa1 , R aa2 and R aa3 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. aa1 , R aa2 and R aa3 The aromatic hydrocarbon group preferably has 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms.

[0012] Examples of the substituent of the alkyl group having 1 to 8 carbon atoms which may have a substituent include an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 18 carbon atoms. Examples of the substituent of the alkenyl group having 2 to 8 carbon atoms which may have a substituent include an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 18 carbon atoms. Examples of the substituent of the alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an aromatic hydrocarbon group having 6 to 18 carbon atoms. Examples of the substituent of the aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an alicyclic hydrocarbon group having 3 to 20 carbon atoms. More specifically, a group obtained by combining the above-described alkyl group and alicyclic hydrocarbon group (for example, an alkylcycloalkyl group or cycloalkylalkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornil group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc.), an aralkyl group such as benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), an aryl-cycloalkyl group such as phenylcyclohexyl group, etc. are included. naa is preferably 1.

[0013] R aa1 and R aa2 When they are bonded to each other to form an alicyclic hydrocarbon group together with a carbon atom, examples of -C(R aa1 )(R aa2 )(R aa3 ) include the following groups. The alicyclic hydrocarbon group is preferably 3 to 16, more preferably 3 to 12 carbon atoms. * represents a bond to -O-. TIFF0007704551000015.tif30140

[0014] Examples of the group represented by the formula (1a) include a 1,1-dialkylalkoxycarbonyl group (in the formula (1a), a group in which R aa1 , R aa2 and R aa3 are alkyl groups, preferably a tert-butoxycarbonyl group), a 2-alkyladamantan-2-yloxycarbonyl group (in the formula (1a), a group in which R aa1 , R aa2 and the carbon atom to which they are attached form an adamantyl group, and R aa3 is an alkyl group), and a 1-(adamantan-1-yl)-1-alkylalkoxycarbonyl group (in the formula (1a), a group in which R aa1 and R aa2 are alkyl groups, and R aa3 is an adamantyl group), etc.

[0015] Examples of the hydrocarbon groups of R aa1' , R aa2' and R aa3' include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these. Examples of the alkyl group and the alicyclic hydrocarbon group are the same as those exemplified for R aa1 , R aa2 and R aa3 . 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. Examples of the combined group include a group combining the above-described alkyl group and alicyclic hydrocarbon group (e.g., cycloalkylalkyl group or alkylcycloalkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornil group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc.), aralkyl group such as benzyl group, aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group such as phenylcyclohexyl group, etc. R aa2' and R aa3' are bonded to each other and, together with the carbon atom to which they are bonded and X a form a heterocyclic group, -C(R aa1' )(R aa2' )-X a -(R aa3' ) includes the following groups. * represents a bond. TIFF0007704551000016.tif20143R aa1' and R aa2' at least one of which is preferably a hydrogen atom.

[0016] Specific examples of the acid-labile group (1a) include the following groups. * represents a bond. TIFF0007704551000017.tif110168

[0017] Specific examples of the acid-labile group (2a) include the following groups. * represents a bond. TIFF0007704551000018.tif87165R 11 is preferably a hydrogen atom or an acid-labile group (1a). R 1 R 2 and R 3 The bonding positions of are each X1 , X 2 and X 3 may be in the ortho, meta, or para position with respect to the bonding position. Among them, X 1 , X 2 and X 3 are preferably bonded in the para position with respect to the bonding position. R 1 , R 2 and R 3 are each independently a hydroxy group, -O-R 10 or -O-L 1 -CO-O-R 10 is preferred, and -O-L 1 -CO-O-R 10 is more preferred.

[0018] R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Examples of the halogen atoms of R R 4 , R 5 , R 6 , R 7 , R 8 and R 9 include fluorine atom, chlorine atom, bromine atom, iodine atom, etc. The C1-C6 fluoroalkyl group of R R 4 , R 5 , R 6 , R 7 , R 8 and R 9Examples 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 either monocyclic or polycyclic, and examples include the groups represented below. The bonding site can be at any position. TIFF0007704551000019.tif41165Specifically, 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 and the like. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group and the like. 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.

[0019] Examples of the group formed by combination include a group formed by combining an aromatic hydrocarbon group and an aliphatic hydrocarbon group (e.g., aromatic hydrocarbon group - alkane diyl group - *, alkyl group - aromatic hydrocarbon group - *, where -CH2- contained in the alkane diyl group and the alkyl group may be replaced by -O-, -CO-, -S- or -SO2-), a group formed by combining an alicyclic hydrocarbon group and an aliphatic hydrocarbon group (e.g., alicyclic hydrocarbon group - alkane diyl group - *, alkyl group - alicyclic hydrocarbon group - *, where -CH2- contained in the alkane diyl group and the alkyl group may be replaced by -O-, -CO-, -S- or -SO2-), and a group formed by 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 and the like. 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 and the like. Examples of the alkyl group - alicyclic hydrocarbon group - * include cycloalkyl groups having an alkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, 2-alkyladamantan-2-yl group and the like. Examples of the aromatic hydrocarbon group - alicyclic hydrocarbon group - * include phenylcyclohexyl group and the like. Examples of the alicyclic hydrocarbon group - aromatic hydrocarbon group - * include cyclohexylphenyl group and the like. In the combination, two or more alicyclic hydrocarbon groups, aromatic hydrocarbon groups and aliphatic hydrocarbon groups may be combined respectively. Also, any of the groups may be bonded to the benzene ring.

[0020] Examples of a group in which -CH2- contained in a hydrocarbon group is replaced by -O-, -CO-, -SO2- or -S- include a hydroxy group (a group in which -CH2- contained in a methyl group is replaced by -O-), a carboxy group (a group in which -CH2-CH2- contained in an ethyl group is replaced by -O-CO-), a thiol group (a group in which -CH2- contained in a methyl group is replaced by -S-), an alkoxy group (a group in which -CH2- at any position contained in an alkyl group is replaced by -O-), an alkoxycarbonyl group (a group in which -CH2-CH2- at any position contained in an alkyl group is replaced by -O-CO-), an alkylthio group (a group in which -CH2- at any position contained in an alkyl group is replaced by -S-), a sulfide (a group in which -CH2- at any position contained in an alkyl group is replaced by -S-), an alkylcarbonyl group (a group in which -CH2- at any position contained in an alkyl group is replaced by -CO-), an alkylcarbonyloxy group (a group in which -CH2-CH2- at any position contained in an alkyl group is replaced by -CO-O-), an alkylsulfonyl group (a group in which -CH2- at any position contained in an alkyl group is replaced by -SO2-), 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. 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, a phenyloxy 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. The alkoxycarbonyl group, the alkylcarbonyl group and the 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, a butoxycarbonyl group and the like. 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.

[0021] 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 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. 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.

[0022] In addition, examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -CO-, -SO2- or -S- include the groups represented below. The -O- in the groups represented below may be replaced by -S-, and -CO- may be replaced by -SO2-. The bonding site can be at any position. When -CH2- contained in the hydrocarbon group is replaced by -O- or -CO-, the number of carbon atoms before replacement is defined as the total number of carbon atoms of the hydrocarbon group. Also, the number may be one or two or more.

[0023] R 4 、R 5 、R 6 、R 7 、R 8 and R 9 Examples of the substituent that the hydrocarbon group of R, R, R, R, R, R, and R may have include a halogen atom, a cyano group, and an alkyl group having 1 to 12 carbon atoms (the -CH2- contained in the alkyl group may be replaced by -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. When -CH2- contained in the alkyl group is replaced by -O- or -CO- as a substituent, 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.

[0024] X 1 is preferably an oxygen atom. X 2 is preferably an oxygen atom. X 3is preferably an oxygen atom. X 1 and X 2 and X 3 may be bonded to the bonding position of S + at any of the ortho, meta, or para positions relative to the bonding position of S. Among them, it is preferably bonded to the para or meta position relative to the bonding position of S + , and more preferably bonded to the para position. m1 is preferably 1 or 2, and more preferably 1. m2 is 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 0. m5 is preferably 0 or 1, and more preferably 0. m6 is preferably 0 or 1, and more preferably 0. m7 is preferably 0, 1, or 2, and more preferably 0. m8 is preferably 0 or 1. When m2 is 0, m8 is preferably 1. m9 is preferably 0 or 1. When m3 is 0, m9 is preferably 1. R 4 and R 5 and R 6 are each independently preferably a halogen atom, a C1-C4 fluoroalkyl group, or a C1-C6 alkyl group (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), more preferably a halogen atom, a C1-C4 fluoroalkyl group, or a C1-C4 alkyl group (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), and even more preferably a C1-C4 alkyl group. R 7 and R 8 and R 9is each independently preferably a halogen atom, a C1-C4 fluoroalkyl group or a C1-C6 alkyl group (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), more preferably a halogen atom, a C1-C4 fluoroalkyl group or a C1-C4 alkyl group (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), still more preferably a fluorine atom, a C1-C4 perfluoroalkyl group or a C1-C4 alkyl group (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), and even more preferably a fluorine atom, a trifluoromethyl group, a methyl group, a t-butyl group, a hydroxy group or a methoxy group.

[0025] Examples of the cation of salt (I) include cations represented by the following formulas (I-c-1) to (I-c-40). TIFF0007704551000021.tif161158

[0026] TIFF0007704551000022.tif239163

[0027] TIFF0007704551000023.tif237153

[0028] TIFF0007704551000024.tif219163

[0029] 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. -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. Examples of the alkyl group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group, etc. The number of carbon atoms in 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. Examples of the group in which -CH2- contained in the chain hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include hydroxy group (the group in which -CH2- contained in the methyl group is replaced by -O-), carboxy group (the group in which -CH2-CH2- contained in the ethyl group is replaced by -O-CO-), thiol group (the group in which -CH2- contained in the methyl group is replaced by -S-), alkoxy group (the group in which -CH2- at any position contained in the alkyl group is replaced by -O-), alkoxycarbonyl group (the group in which -CH2-CH2- at any position contained in the alkyl group is replaced by -O-CO-), alkylcarbonyl group (the group in which -CH2- at any position contained in the alkyl group is replaced by -CO-), alkylcarbonyloxy group (the group in which -CH2-CH2- at any position contained in the alkyl group is replaced by -CO-O-), alkylthio group (the group in which -CH2- at any position contained in the alkyl group is replaced by -S-), etc. Examples of the alkoxy group, alkoxycarbonyl group, sulfide, alkylcarbonyl group, alkylcarbonyloxy group, and alkylthio group include the same groups as described above. In the alkenyl group and alkynyl group, the substitution may be any one that contains a carbon-carbon double bond or a carbon-carbon triple bond at an arbitrary position in the examples of the substitution in the above-described alkyl group.

[0030] The alicyclic hydrocarbon group may be monocyclic, polycyclic, or spirocyclic, and may be saturated or unsaturated. Examples of the alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclododecyl group, and polycyclic cycloalkyl groups such as norbornyl group and adamantyl group. Specific examples of the group in which the alicyclic hydrocarbon group or -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO-, or -SO2- include the following groups, etc. The bonding site can be at any position. TIFF0007704551000025.tif79161

[0031] As the alicyclic hydrocarbon group or the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2-, the groups represented by formulae (y1) to (y71) are preferable, the groups represented by any of formulae (y1) to (y20), formula (y26), formula (y27), formula (y30), formula (y31), formulae (y39) to (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), formulae (y49) to (y58), formulae (y62) to (y71) are even more preferable. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 36, more preferably 3 to 24, even more preferably 3 to 18, still more preferably 3 to 16, and yet even more preferably 3 to 12.

[0032] 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, even more preferably 6 to 18, still more preferably 6 to 14, and yet 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.

[0033] The combined group means a group formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group (the -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), a group formed by combining a chain hydrocarbon group and an aromatic hydrocarbon group (the -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), and A group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). In the combination, two or more kinds of alicyclic hydrocarbon groups, chain hydrocarbon groups and aromatic hydrocarbon groups may be combined respectively. Specifically, examples of the combined group include An alicyclic hydrocarbon group - chain hydrocarbon group - *, such as an adamantylmethylene group or a cyclohexylmethylene group, ((alicyclic hydrocarbon group)2 - chain hydrocarbon group - *) (wherein -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). A chain hydrocarbon group - alicyclic hydrocarbon group - *, such as a methyladamantyl group or a dimethyladamantyl group, ((chain hydrocarbon group)2 - alicyclic hydrocarbon group - *) (wherein -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). A chain hydrocarbon group - aromatic hydrocarbon group - *, such as a tolyl group or a xylyl group (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). A chain hydrocarbon group - alicyclic hydrocarbon group - chain hydrocarbon group - *, such as a methylcyclohexylmethylene group, ((chain hydrocarbon group)2 - alicyclic hydrocarbon group - chain hydrocarbon group - *), ((chain hydrocarbon group - alicyclic hydrocarbon group)2 - chain hydrocarbon group - *) (wherein -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). An aromatic hydrocarbon group - chain hydrocarbon group - *, such as a benzyl group (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). A chain hydrocarbon group - aromatic hydrocarbon group - chain hydrocarbon group - *, such as a tolylmethyl group (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). 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 - * (wherein -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), 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 - * (wherein -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), 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 - * (wherein -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), etc. Here, * represents the bonding position with the carbon atom of the carbonyl group.

[0034] X 0 When -CH2- contained in the hydrocarbon group represented by is replaced by -O-, -S-, -CO- or -SO2-, the carbon number before replacement is taken as the total carbon number of the hydrocarbon group. Also, X 0When a substituent is bonded to the hydrocarbon group represented by , the total number of carbon atoms before substitution is defined as the total 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, etc. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, etc. The alkoxycarbonyl group having 2 to 13 carbon atoms, the alkylcarbonyl group having 2 to 13 carbon atoms, and the alkylcarbonyloxy group having 2 to 13 carbon atoms represent 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 having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc. Examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, a butyryl group, etc. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, a 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 represents the bonding position with . As the aromatic hydrocarbon group having 6 to 10 carbon atoms in TIFF0007704551000027.tif17162, aryl groups such as phenyl group and naphthyl group can be mentioned. As the combined group, groups obtained by combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms, groups obtained by combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, groups obtained by combining an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, etc. can be mentioned. As the group obtained by combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms, hydroxyalkyl groups having 1 to 12 carbon atoms such as hydroxymethyl group and hydroxyethyl group can be mentioned. As the group obtained by combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, aralkyl groups having 7 to 22 carbon atoms such as benzyl group, and alkylaryl groups having 7 to 22 carbon atoms such as tolyl group and xylyl group can be mentioned. As the group obtained by combining an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, cyclohexylphenyl group etc. can be mentioned.

[0035] X 0 As the hydrocarbon group represented by, preferably, an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (wherein -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent, More preferably, it is an alicyclic hydrocarbon group having 1 to 36 carbon atoms which may have a hydroxy group or a fluorine atom (however, -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), a group combining an alicyclic hydrocarbon group having 1 to 36 carbon atoms and a chain hydrocarbon group having 1 to 18 carbon atoms ( -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group), a halogen atom, a hydroxy group, or an aromatic hydrocarbon group having 6 carbon atoms which may have a perfluoroalkyl group having 1 to 4 carbon atoms, Even more preferably, it is a *-alicyclic hydrocarbon group ( -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom. * represents the bonding position to the carbon atom of -COO - .), a *-alicyclic hydrocarbon group-chain hydrocarbon group ( -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group. * represents the bonding position to the carbon atom of -COO - .), a *-chain hydrocarbon group-alicyclic hydrocarbon group ( -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the chain hydrocarbon group and the alicyclic hydrocarbon group may have a fluorine atom or a hydroxy group. * represents the bonding position to the carbon atom of -COO - .), 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), More preferably, it is a polycyclic alicyclic hydrocarbon group (the -CH2- contained in the polycyclic alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the polycyclic alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom. * is -COO - represents the bonding position with the carbon atom of). A polycyclic alicyclic hydrocarbon group - a chain hydrocarbon group (the -CH2- contained in the polycyclic alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the polycyclic alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group. * is -COO - represents the bonding position with the carbon atom of). A chain hydrocarbon group - a polycyclic alicyclic hydrocarbon group (the -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the -CH2- contained in the polycyclic alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the chain hydrocarbon group and the polycyclic alicyclic hydrocarbon group may have a fluorine atom or a hydroxy group. * is -COO - represents the bonding position with 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 (the -CH2- contained in the alkyl group may be replaced by -O- or -CO-), a group represented by formula (Y30F), or a phenyl group having a hydroxy group.

[0036] Based on the above, the number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 36, more preferably 3 to 24, still more preferably 3 to 18, even more preferably 3 to 16, and even more preferably 3 to 12. The number of carbon atoms in the chain hydrocarbon group is preferably 1 to 18, more preferably 1 to 12, still more preferably 1 to 9, even more preferably 1 to 6, and even more preferably 1 to 4. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 36, more preferably 6 to 24, still more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. TIFF0007704551000028.tif26127[In formula (aa), X a and X b each independently represents -O- or -S-. X 1a represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. X 2a represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. * represents the bonding position with the carbon atom of -COO - .] [In formula (bb), L A represents an alkanediyl group having 1 to 6 carbon atoms which may have a fluorine atom, or an aromatic hydrocarbon group having 6 carbon atoms which may have a halogen atom or a perfluoroalkyl group having 1 to 4 carbon atoms. L B represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, and -CH2- contained in the alkanediyl group may be replaced by -O-, -S-, -CO- or -SO2-. R Arepresents a hydrocarbon group having 1 to 36 carbon atoms which may have substituents, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. * represents the bonding position with the carbon atom of -COO - .

[0037] X a and X b are preferably the same atom, and more preferably both are oxygen atoms.

[0038] X 1a and X 2a Examples of the hydrocarbon group represented by X 1a and X 2a include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group formed by combining two or more of these. Note that these hydrocarbon groups may have substituents. In addition, -CH2- contained in these hydrocarbon groups may be replaced by -O-, -S-, -CO- or -SO2-. Here, the number of carbon atoms of the hydrocarbon group means the number of carbon atoms of the hydrocarbon group having no substituents and no replacements.

[0039] X 1a Examples of the aliphatic hydrocarbon group of X 1a include a chain hydrocarbon group such as an alkanetriyl group, an alicyclic hydrocarbon group, or a group formed by combining these. Specific examples of the alkanetriyl group include a methine group, an ethanetriyl group, a propanetriyl group, a butanetriyl group, a pentanetriyl group, a hexanetriyl group, a heptanetriyl group, an octanetriyl group, a nonanetriyl group, a decanetriyl group, an undecanetriyl group, a dodecanetriyl group, and the like.

[0040] The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclobutanetriyl group, a cyclopentanetriyl group, a cyclohexanetriyl group, a cyclooctanetriyl group, and the like. Examples of the polycyclic alicyclic hydrocarbon group include a norbornanetriyl group, an adamantanetriyl group, and the like. Examples of the aromatic hydrocarbon group include a benzene triyl group, a naphthalene triyl group, an anthracene triyl group, and the like. In the case of a combined group, a group having a different valence number in the above-mentioned groups (such as an alkyl group, an alkane diyl group, an alkane tetrayl group, a cycloalkyl group, a cycloalkane diyl group, a cycloalkane tetrayl group, etc.) may be included.

[0041] X 1a The hydrocarbon group represented by [X] has 1 to 24 carbon atoms and may further have one or more substituents. Examples of the substituent include a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group obtained by combining these. Examples of the halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and a group obtained by combining these are the same as those described above.

[0042] 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). TIFF0007704551000029.tif54143 [In formula (w1-1) to formula (w1-11), The ring may have a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group combining these. * represents a bonding position.

[0043] X 2a The hydrocarbon group represented by is preferably 2 to 48 carbon atoms, more preferably 4 to 48 carbon atoms, still more preferably 6 to 44 carbon atoms, even more preferably 8 to 40 carbon atoms, and even still more preferably 10 to 38 carbon atoms.

[0044] X 2a Examples of the substituent that the hydrocarbon group in 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 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 combining these are the same as those described above. X 2a The hydrocarbon group having 1 to 48 carbon atoms represented by may have one substituent or a plurality of substituents.

[0045] X 2a Examples of the hydrocarbon group in include a linear or branched chain hydrocarbon group (e.g., an alkanediyl group, etc.), a monocyclic or polycyclic alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and those combining two or more of these groups may also be used. Specifically, linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group; Branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; Monocyclic alicyclic hydrocarbon groups which are monocyclic 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 alicyclic hydrocarbon groups which are polycyclic cycloalkanediyl groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group; Aromatic hydrocarbon groups such as phenylene group, naphthylene group, biphenylene group, anthrylene group, phenanthrylene group, binaphthylene group, etc. can be mentioned. In the case of a combined group, groups with different valences (alkyl group, alkanetriyl group, alkanetetrayl group, cycloalkyl group, cycloalkanetriyl group, cycloalkanetetrayl group, etc.) in the above-mentioned groups may be included. Examples of the combined group include a group combining an aliphatic hydrocarbon group and an alicyclic hydrocarbon group, a group combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group, a group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group, etc. Specifically, a group in which one or more alicyclic hydrocarbon groups are bonded to an aliphatic hydrocarbon group (for example, -aliphatic hydrocarbon group - alicyclic hydrocarbon group, -aliphatic hydrocarbon group -(alicyclic hydrocarbon group)2, etc.), a group in which one or more aliphatic hydrocarbon groups are bonded to an alicyclic hydrocarbon group (for example, -alicyclic hydrocarbon group - aliphatic hydrocarbon group, -alicyclic hydrocarbon group -(aliphatic hydrocarbon group)2, etc.), a group in which one or more alicyclic hydrocarbon groups and aliphatic hydrocarbon groups are bonded to an aliphatic hydrocarbon group (for example, -aliphatic hydrocarbon group - alicyclic hydrocarbon group - aliphatic hydrocarbon group, -aliphatic hydrocarbon group -(alicyclic hydrocarbon group - aliphatic hydrocarbon group)2, etc.), and the like can be mentioned.

[0046] X 2a As the hydrocarbon group in, an aliphatic hydrocarbon group having 2 to 18 carbon atoms (the -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O- or -CO-, and the aliphatic hydrocarbon group may have a substituent), an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the alicyclic hydrocarbon group may have a substituent), or a group combining an aliphatic hydrocarbon group having 1 to 12 carbon atoms (the -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) (the group may have a substituent) is preferable, an aliphatic hydrocarbon group having 4 to 18 carbon atoms (the -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O- or -CO-, and the aliphatic hydrocarbon group may have a substituent), or A group formed by combining an acyclic hydrocarbon group having 1 to 12 carbon atoms (wherein -CH2- contained in the acyclic hydrocarbon group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) (the group may have a substituent) is more preferable. An acyclic hydrocarbon group having 6 to 14 carbon atoms (wherein -CH2- contained in the acyclic hydrocarbon group may be replaced by -O- or -CO-, and the acyclic hydrocarbon group may have a substituent), or A group formed by combining an acyclic hydrocarbon group having 1 to 12 carbon atoms (wherein -CH2- contained in the acyclic hydrocarbon group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 5 to 14 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) (the group may have a substituent) is even more preferable.

[0047] Specifically, the hydrocarbon group in X 2a is, for example, An alkanediyl group having 2 to 18 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-, and the alkanediyl group may have a substituent), An alicyclic hydrocarbon group having 3 to 18 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the alicyclic hydrocarbon group may have a substituent), A group composed of an alkanediyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) (the group may have a substituent), or A group composed of an alkanediyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and an alkyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-) (the group may have a substituent) is preferred. An alkanediyl group having 4 to 18 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-, and the alkanediyl group may have a substituent). A group composed of an alkanediyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) (the group may have a substituent), or A group composed of an alkanediyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 16 carbon atoms, and an alkyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-) (the group may have a substituent) is more preferred. An alkanediyl group having 6 to 14 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-, and the alkanediyl group may have a substituent). A group composed of an alkanediyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-) and an adamantanediyl group (wherein -CH2- contained in the adamantanediyl group may be replaced by -O- or -CO-) (the group may have a substituent), or An alkandiyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkandiyl group may be replaced by -O- or -CO-), an adamantandiyl group, and an alkyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-). It is more preferable that the group may have a substituent.

[0048] More specifically, X 2a is 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). TIFF0007704551000030.tif35158[In the formula, R 1x 、R 2x 、R 3x 、R 4x 、R 5x and R 6x each independently represents an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by combining two or more of these groups. -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the alkyl group and the alicyclic hydrocarbon group may have a substituent. * represents the bonding position with X a and X b .] The combined group may be 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.

[0049] Among them, R 1x 、R 2x 、R 3x 、R 4x 、R 5x and R 6xExamples thereof include an alkyl group having 1 to 6 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-, and the alkyl group may have a substituent), an alicyclic hydrocarbon group having 5 to 12 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the alicyclic hydrocarbon group may have a substituent), or a group formed by combining an alkyl group having 1 to 6 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 5 to 12 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) (the group may have a substituent). Preferably, it is a methoxy group, an adamantyl group (wherein -CH2- contained in the adamantyl group may be replaced by -O- or -CO-, and the adamantyl group may have a substituent), or a group formed by combining an alkyl group having 1 to 6 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-) and an adamantyl group (the group may have a substituent). More preferably, it is such a group.

[0050] In formula (bb), L A and L B Examples of the alkanediyl group having 1 to 6 carbon atoms include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group; and branched alkanediyl groups such as a propane-1,2-diyl group, a 1-methylpropane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a 1-methylbutane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. The number of carbon atoms of the alkanediyl group is preferably 1 to 4, more preferably 1 to 3. Examples of the alkanediyl group which may have a fluorine atom include perfluoroalkanediyl groups such as a difluoromethylene group, a perfluoroethylene group, a perfluoropropanediyl group, a perfluorobutanediyl group, and a perfluoropentanediyl group. When -CH2- contained in the alkanediyl group is replaced by -O- or -CO-, the total number of carbon atoms before replacement is defined as the total number of carbon atoms of the alkanediyl group. The alkanediyl group may have a hydroxy group (a group in which -CH2- contained in a methyl group is replaced by -O-), a carboxy group (a group in which -CH2-CH2- contained in an ethyl group is replaced by -O-CO-), an alkoxy group (a group in which any -CH2- contained in an alkyl group is replaced by -O-), an alkoxycarbonyl group (a group in which any -CH2-CH2- contained in an alkyl group is replaced by -O-CO-), an alkylcarbonyl group (a group in which any -CH2- contained in an alkyl group is replaced by -CO-), an alkylcarbonyloxy group (a group in which any -CH2-CH2- contained in an alkyl group is replaced by -CO-O-), an alkanediyl-oxy group (a group in which any -CH2- contained in an alkanediyl group is replaced by -O-), an alkanediyl-oxycarbonyl group (a group in which any -CH2-CH2- contained in an alkanediyl group is replaced by -O-CO-), an alkanediylcarbonyl group (a group in which any -CH2- contained in an alkanediyl group is replaced by -CO-), or an alkanediylcarbonyloxy group (a group in which any -CH2-CH2- contained in an alkanediyl group is replaced by -CO-O-). Examples of the alkanediyl-oxy group include a methylene-oxy group, an ethylene-oxy group, a propanediyl-oxy group, a butanediyl-oxy group, and a pentanediyl-oxy group. Examples of the alkanediyl-oxycarbonyl group include a methylene-oxycarbonyl group, an ethylene-oxycarbonyl group, a propanediyl-oxycarbonyl group, and a butanediyl-oxycarbonyl group. Examples of the alkanediylcarbonyl group include a methylenecarbonyl group, an ethylenecarbonyl group, a propanediylcarbonyl group, a butanediylcarbonyl group, a pentanediylcarbonyl group, and the like. Examples of the alkanediylcarbonyloxy group include a methylenecarbonyloxy group, an ethylenecarbonyloxy group, a propanediylcarbonyloxy group, a butanediylcarbonyloxy group, and the like. L A is preferably an alkanediyl group having 1 to 4 carbon atoms which may have a fluorine atom, and more preferably an alkanediyl group having 1 to 3 carbon atoms having a fluorine atom. L B is preferably a single bond or an alkanediyl group having 1 to 3 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), and more preferably a single bond, a methylene group or an ethylene group.

[0051] R A Examples of the hydrocarbon group in R include an aliphatic hydrocarbon group (a chain hydrocarbon group such as an alkyl group, an alkenyl group, an alkynyl group, and an alicyclic hydrocarbon group), an aromatic hydrocarbon group, and a group formed by combining these. Examples of the alkyl group include 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, an n-hexyl group, an n-heptyl group, a 2-ethylhexyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an 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 an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, an isooctenyl group, a 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. Examples of the group in which -CH2- contained in the chain hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include hydroxy group, carboxy group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alkylthio group and the like. Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group and alkylthio group include, for example, an alkoxy group having 1 to 17 carbon atoms, an alkoxycarbonyl group having 2 to 17 carbon atoms, an alkylcarbonyl group having 2 to 18 carbon atoms, an alkylcarbonyloxy group having 2 to 17 carbon atoms, and an alkylthio group having 1 to 17 carbon atoms, and groups similar to the above-described groups. The alicyclic hydrocarbon group may be monocyclic, polycyclic or spiro ring, and may be saturated or unsaturated. Examples of the monocyclic alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclododecyl group and the like. Examples of the polycyclic alicyclic hydrocarbon group include polycyclic cycloalkyl groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the like. Specific examples of the alicyclic hydrocarbon group and the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- 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 phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, and binaphthyl group. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 36, more preferably 6 to 24, still more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. In the case of a combined group, groups with different valences in the above-mentioned groups (such as alkanediyl group, alkanetriyl group, cycloalkanediyl group, cycloalkanetriyl group, etc.) may be included. Examples of the group formed by combination include a group combining an aromatic hydrocarbon group and a chain hydrocarbon group (for example, aromatic hydrocarbon group - alkanediyl group - *, alkyl group - aromatic hydrocarbon group - *), a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (for example, alicyclic hydrocarbon group - alkanediyl group - *, alkyl group - alicyclic hydrocarbon group - *), and a group combining an aromatic hydrocarbon group and an alicyclic hydrocarbon group (for example, aromatic hydrocarbon group - alicyclic hydrocarbon group - *, alicyclic hydrocarbon group - aromatic hydrocarbon group - *). * represents a bonding site. Examples of the aromatic hydrocarbon group - alkanediyl group - * include aralkyl groups such as benzyl group and phenethyl group. Examples of the alkyl group - aromatic hydrocarbon group - * include tolyl group, xylyl group, cumenyl group, etc. Examples of the alicyclic hydrocarbon group - alkanediyl group - * include cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, and 1-(adamantan-1-yl)-1-methylethyl. Examples of the alkyl group - alicyclic hydrocarbon group - * include cycloalkyl groups having an alkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, and 2-alkyladamantan-2-yl group. 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 thereof. Further, any of the groups may be bonded to L B .

[0052] Examples of the group in which -CH2- contained in the hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include, in addition to the above-described groups, a cycloalkoxy group, a cycloalkylalkoxy group, an alkoxycarbonyloxy group, an aromatic hydrocarbon group-carbonyl oxy group, and a group formed 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. When -CH2- contained in the hydrocarbon group is replaced by -O-, -S-, -SO2- or -CO-, the total number of carbon atoms before replacement is defined as the total number of carbon atoms of the hydrocarbon group. Also, the number may be one or two or more.

[0053] R A Examples of the substituent that the hydrocarbon group of may have include a halogen atom, a cyano group, and an alkyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O-, -S-, -CO- or -SO2-). Examples of the halogen atom include the same groups as those described above. Examples of the alkyl group having 1 to 12 carbon atoms include the same groups as those described above. Examples of the group in which -CH2- contained in the alkyl group is replaced by -O- or -CO- include a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, and the like. Examples of the alkoxy group, the alkoxycarbonyl group, the alkylcarbonyl group, and the alkylcarbonyloxy group include an alkoxy group having 1 to 11 carbon atoms, an alkoxycarbonyl group having 2 to 11 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, and an alkylcarbonyloxy group having 2 to 11 carbon atoms. For example, groups similar to the above-described groups can be mentioned. R A The hydrocarbon group in R may have one substituent or a plurality of substituents.

[0054] R A Examples of the hydrocarbon group in R include an alkyl group having 1 to 12 carbon atoms which may have a substituent (however, -CH2- contained in the alkyl group may be replaced by -O-, -S-, -CO- or -SO2-), or a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (however, -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). Preferably, it is a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 6 carbon atoms (however, -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-).

[0055] Examples of the cyclic hydrocarbon group include cyclic hydrocarbon groups such as monocyclic or polycyclic alicyclic hydrocarbon groups having 3 to 18 carbon atoms and aromatic hydrocarbon groups having 6 to 18 carbon atoms, or groups combining these. Examples of the alicyclic hydrocarbon group, the aromatic hydrocarbon group, and the combined group are the same as those described above. In the combination, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be combined with two or more of each. Also, any of the groups may be bonded to L B and may be bonded thereto.

[0056] 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 -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), 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 ( -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), 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 ( -CH2- contained in the alicyclic hydrocarbon group 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. TIFF0007704551000031.tif1687

[0057] Examples of the carboxylic acid anion in the carboxylate represented by the formula (I) include the carboxylic acid anions described below. TIFF0007704551000032.tif140165

[0058] TIFF0007704551000033.tif236168

[0059] TIFF0007704551000034.tif72168

[0060] TIFF0007704551000035.tif163163

[0061] TIFF0007704551000036.tif173161

[0062] Specific examples of the carboxylate (I) include salts obtained by arbitrarily combining the above-mentioned cations and anions. Specific examples of the carboxylate (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). TIFF0007704551000037.tif31125

[0063] [Table 1]

[0064] Among them, as the carboxylate (I), A salt formed by combining an anion represented by any one of formula (I-a-1) to formula (I-a-5), formula (I-a-10) to formula (I-a-21), and formula (I-a-57) to formula (I-a-66) with a cation represented by any one of formula (I-c-1) to formula (I-c-40) is preferred. Specifically, carboxylic salts (I-1) to carboxylic salts (I-5), carboxylic salts (I-10) to carboxylic salts (I-21), carboxylic salts (I-57) to carboxylic salts (I-66), carboxylic salts (I-96) to carboxylic salts (I-100), carboxylic salts (I-105) to carboxylic salts (I-116), carboxylic salts (I-152) to carboxylic salts (I-161), carboxylic salts (I-191) to carboxylic salts (I-195), carboxylic salts (I-200) to carboxylic salts (I-211), carboxylic salts (I-247) to carboxylic salts (I-256), carboxylic salts (I-286) to carboxylic salts (I-290), carboxylic salts (I-295) to carboxylic salts (I-306), carboxylic salts (I-342) to carboxylic salts (I-351), carboxylic salts (I-381) to carboxylic salts (I-385), carboxylic salts (I-390) to carboxylic salts (I-401), carboxylic salts (I-437) to carboxylic salts (I-446), carboxylic salts (I-476) to carboxylic salts (I-480), carboxylic salts (I-485) to carboxylic salts (I-496), carboxylic salts (I-532) to carboxylic salts (I-541), carboxylic salts (I-571) to carboxylic salts (I-575), carboxylic salts (I-580) to carboxylic salts (I-591), carboxylic salts (I-627) to carboxylic salts (I-636), carboxylic salts (I-666) to carboxylic salts (I-670), carboxylic salts (I-675) to carboxylic salts (I-686), carboxylic salts (I-722) to carboxylic salts (I-731), carboxylic salts (I-761) to carboxylic salts (I-765), carboxylic salts (I-770) to carboxylic salts (I-781), carboxylic salts (I-817) to carboxylic salts (I-826), carboxylic salts (I-856) to carboxylic salts (I-860), carboxylic salts (I-865) to carboxylic salts (I-876), carboxylic salts (I-912) to carboxylic salts (I-921), carboxylic salts (I-951) to carboxylic salts (I-955), carboxylic salts (I-960) to carboxylic salts (I-971), carboxylic salts (I-1007) to carboxylic salts (I-1016).Carboxylate (I-1046) to Carboxylate (I-1050), Carboxylate (I-1055) to Carboxylate (I-1066), Carboxylate (I-1102) to Carboxylate (I-1111), Carboxylate (I-1141) to Carboxylate (I-1145), Carboxylate (I-1150) to Carboxylate (I-1161), Carboxylate (I-1197) to Carboxylate (I-1206), Carboxylate (I-1236) to Carboxylate (I-1240), Carboxylate (I-1245) to Carboxylate (I-1256), Carboxylate (I-1292) to Carboxylate (I-1301), Carboxylate (I-1331) to Carboxylate (I-1335), Carboxylate (I-1340) to Carboxylate (I-1351), Carboxylate (I-1387) to Carboxylate (I-1396), Carboxylate (I-1426) to Carboxylate (I-1430), Carboxylate (I-1435) to Carboxylate (I-1446), Carboxylate (I-1482) to Carboxylate (I-1491), Carboxylate (I-1521) to Carboxylate (I-1525), Carboxylate (I-1530) to Carboxylate (I-1541), Carboxylate (I-1577) to Carboxylate (I-1586), Carboxylate (I-1616) to Carboxylate (I-1620), Carboxylate (I-1625) to Carboxylate (I-1636), Carboxylate (I-1672) to Carboxylate (I-1681), Carboxylate (I-1711) to Carboxylate (I-1715), Carboxylate (I-1720) to Carboxylate (I-1731), Carboxylate (I-1767) to Carboxylate (I-1776), Carboxylate (I-1806) to Carboxylate (I-1810), Carboxylate (I-1815) to Carboxylate (I-1826), Carboxylate (I-1862) to Carboxylate (I-1871), Carboxylate (I-1901) to Carboxylate (I-1905), Carboxylate (I-1910) to Carboxylate (I-1921), Carboxylate (I-1957) to Carboxylate (I-1966), Carboxylate (I-1996) to Carboxylate (I-2000), Carboxylate (I-2005) to Carboxylate (I-2016), Carboxylate (I-2052) to Carboxylate (I-2061), Carboxylate (I-2091) to Carboxylate (I-2095), Carboxylate (I-2100) to Carboxylate (I-2111)Carboxylate (I-2147) to Carboxylate (I-2156), Carboxylate (I-2186) to Carboxylate (I-2190), Carboxylate (I-2195) to Carboxylate (I-2206), Carboxylate (I-2242) to Carboxylate (I-2251), Carboxylate (I-2281) to Carboxylate (I-2285), Carboxylate (I-2290) to Carboxylate (I-2301), Carboxylate (I-2337) to Carboxylate (I-2346), Carboxylate (I-2376) to Carboxylate (I-2380), Carboxylate (I-2385) to Carboxylate (I-2396), Carboxylate (I-2432) to Carboxylate (I-2441), Carboxylate (I-2471) to Carboxylate (I-2475), Carboxylate (I-2480) to Carboxylate (I-2491), Carboxylate (I-2527) to Carboxylate (I-2536), Carboxylate (I-2566) to Carboxylate (I-2570), Carboxylate (I-2575) to Carboxylate (I-2586), Carboxylate (I-2622) to Carboxylate (I-2631), Carboxylate (I-2661) to Carboxylate (I-2665), Carboxylate (I-2670) to Carboxylate (I-2681), Carboxylate (I-2717) to Carboxylate (I-2726), Carboxylate (I-2756) to Carboxylate (I-2760), Carboxylate (I-2765) to Carboxylate (I-2776), Carboxylate (I-2812) to Carboxylate (I-2821), Carboxylate (I-2851) to Carboxylate (I-2855), Carboxylate (I-2860) to Carboxylate (I-2871), Carboxylate (I-2907) to Carboxylate (I-2916), Carboxylate (I-2946) to Carboxylate (I-2950), Carboxylate (I-2955) to Carboxylate (I-2966), Carboxylate (I-3002) to Carboxylate (I-3011), Carboxylate (I-3041) to Carboxylate (I-3045), Carboxylate (I-3050) to Carboxylate (I-3061), Carboxylate (I-3097) to Carboxylate (I-3106), Carboxylate (I-3136) to Carboxylate (I-3140), Carboxylate (I-3145) to Carboxylate (I-3156), Carboxylate (I-3192) to Carboxylate (I-3201), Carboxylate (I-3231) to Carboxylate (I-3235)Carboxylate (I-3240) to Carboxylate (I-3251), Carboxylate (I-3287) to Carboxylate (I-3296), Carboxylate (I-3326) to Carboxylate (I-3330), Carboxylate (I-3335) to Carboxylate (I-3346), Carboxylate (I-3382) to Carboxylate (I-3391), Carboxylate (I-3421) to Carboxylate (I-3425), Carboxylate (I-3430) to Carboxylate (I-3441), Carboxylate (I-3477) to Carboxylate (I-3486), Carboxylate (I-3516) to Carboxylate (I-3520), Carboxylate (I-3525) to Carboxylate (I-3536), Carboxylate (I-3572) to Carboxylate (I-3581), Carboxylate (I-3611) to Carboxylate (I-3615), Carboxylate (I-3620) to Carboxylate (I-3631), Carboxylate (I-3667) to Carboxylate (I-3676), Carboxylate (I-3706) to Carboxylate (I-3710), Carboxylate (I-3715) to Carboxylate (I-3726), Carboxylate (I-3762) to Carboxylate (I-3771) are preferred.

[0065] <Method for Producing Salt (I)> Salt (I) can be produced by reacting the salt represented by formula (I-a) and the salt represented by formula (I-b) in a solvent. TIFF0007704551000039.tif97163[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.

[0066] The salt represented by formula (I-b) can be synthesized with reference to the methods described in JP-A-2011-39502 and JP-A-2014-88367, and examples thereof include salts represented below. TIFF0007704551000040.tif72163

[0067] TIFF0007704551000041.tif67168

[0068] In salt (I-a), R 1 , R 2 and R 3 are -O-L 1 -CO-O-R 10 The salt represented by formula (I-a1) can be produced by reacting the salt represented by formula (I-c) with the compound represented by formula (I-d) in a solvent in the presence of a base catalyst. TIFF0007704551000042.tif87161[In the formula, all the symbols have the same meanings as described above.] Examples of the base include potassium carbonate, potassium iodide, pyridine, triethylamine and the like. Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, water and the like. The reaction temperature is usually 15°C to 80°C, and the reaction time is usually 0.5 to 24 hours.

[0069] Examples of the compound represented by formula (I-d) include compounds represented below, which can be easily obtained from the market and can also be easily produced by known production methods. TIFF0007704551000043.tif31127

[0070] The salt represented by formula (I-c) can be produced by reacting the salt represented by formula (I-e) with 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. TIFF0007704551000044.tif79130[Wherein, 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 15°C to 100°C, and the reaction time is usually 0.5 to 24 hours.

[0071] 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. TIFF0007704551000045.tif72140

[0072] 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. TIFF0007704551000046.tif1662

[0073] 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, and then subjecting it to acid treatment. TIFF0007704551000047.tif82132[Wherein, all the symbols have the same meanings as described above. R ac represents an acid-labile group.] Examples of the solvent include chloroform, monochlorobenzene, acetonitrile, and water. The reaction temperature is usually 15°C to 100°C, and the reaction time is usually 0.5 to 24 hours. Examples of the acid include p-toluenesulfonic acid and hydrochloric acid.

[0074] 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 the compounds represented below, and they can be easily obtained from the market. TIFF0007704551000048.tif31135

[0075] In salt (I-a), R 1 , R 2 and R 3 are -O-CO-R 10 The salt represented by formula (I-a2) can be produced by reacting the salt represented by formula (I-c) with the compound represented by formula (I-d2) in a solvent in the presence of a base catalyst. TIFF0007704551000049.tif94165[Wherein, all the symbols have the same meanings as described above.] Examples of the base include potassium carbonate, potassium iodide, pyridine, triethylamine and the like. Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, water and the like. The reaction temperature is usually 15°C to 80°C, and the reaction time is usually 0.5 to 24 hours.

[0076] Examples of the compound represented by formula (I-d2) include the compounds represented below, and they can be easily obtained from the market and can also be easily produced by known production methods. TIFF0007704551000050.tif16161

[0077] In salt (I-a), R 1 , R 2 and R 3 are -O-R 10 The salt represented by formula (I-a3) can be produced by reacting the salt represented by formula (I-c) with the compound represented by formula (I-d3) in a solvent in the presence of a base catalyst. TIFF0007704551000051.tif92163[In the formula, all the symbols have the same meanings as described above.] Examples of the base include sodium hydroxide 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.

[0078] Examples of the compound represented by the formula (I-d3) include the compounds represented below, which can be easily obtained from the market and can also be easily produced by known production methods. TIFF0007704551000052.tif16165

[0079] In the salt (I-a), R 1 , R 2 and R 3 being -O-CO-O-R 10 The salt represented by the formula (I-a4) can be produced by reacting the salt represented by the formula (I-c) with the compound represented by the formula (I-d3) in a solvent in the presence of carbonyldiimidazole. TIFF0007704551000053.tif94163[In the formula, all the symbols have the same meanings as described above.] 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.

[0080] 〔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 the carboxylate (I) is used as an acid generator in a resist composition, the acid generator may contain only one kind or two or more kinds 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 content of 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.

[0081] 〔Resist composition〕 The resist composition contains a carboxylic acid generator containing the carboxylate (I) of the present invention, an acid generator (B) other than the carboxylate (I), and a resin having an acid-labile group (hereinafter sometimes referred to as "resin (A)"). The "acid-labile group" here means a group having a leaving group, and when the leaving group is eliminated by contact with an acid, a hydrophilic group (for example, a hydroxy group or a carboxy group) is formed. The resist composition preferably further contains a quencher (hereinafter sometimes referred to as "quencher (C)") and / or a solvent (hereinafter sometimes referred to as "solvent (E)"). In the resist composition of the present invention, the content rate of the carboxylate (I) is preferably 0.1 mass% or more and 35 mass% or less, more preferably 0.5 mass% or more and 30 mass% or less, and still more preferably 1 mass% or more and 25 mass% or less based on the solid content of the resist composition.

[0082] <Acid generator (B)> The acid generator (B) may be either nonionic or ionic. Examples of nonionic acid generators 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), and the like. Representative examples of ionic acid generators include onium salts containing an onium cation (e.g., diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of anions of the onium salts include sulfonic acid anion, sulfonylimide anion, sulfonylmethide anion, and the like.

[0083] As the acid generator (B), compounds that generate an acid upon irradiation, as 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. Further, compounds produced by known methods may also be used. The acid generator (B) may be used in combination of two or more kinds.

[0084] 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)"). TIFF0007704551000054.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, wherein -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-. Z + represents an organic cation.

[0085] Q b1 and Q b2 Examples of the perfluoroalkyl group represented by Q and Q include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, a perfluorohexyl group and the like. Q b1 and Q b2 are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably both are fluorine atoms.

[0086] L b1 Examples of the divalent saturated hydrocarbon group in L include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and a group formed by combining two or more of these groups may also be used. Specifically, linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group and a heptadecane-1,17-diyl group; Branched alkanediyl groups such as 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. can be mentioned.

[0087] L b1 Examples of the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced by -O- or -CO- include groups represented by any of formula (b1-1) to formula (b1-3). In the groups represented by formula (b1-1) to formula (b1-3) and the groups represented by formula (b1-4) to formula (b1-11) which are specific examples thereof, * and ** represent bonding positions, and * represents the bonding position with -Y.

[0088] TIFF0007704551000055.tif26117[In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. However, b2 The total number of carbon atoms of L b3 and L In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, the total number of carbon atoms of L 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 the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, the total number of carbon atoms of L b6 and L b7 is 23 or less.

[0089] In the groups represented by formula (b1-1) to formula (b1-3), when -CH2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-, the number of carbon atoms before replacement is taken as the number of carbon atoms of the saturated hydrocarbon group. Examples of the divalent saturated hydrocarbon group include the same ones as the divalent saturated hydrocarbon group of L b1 .

[0090] L b2 is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms. L b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-.

[0091] L b1 As the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced with -O- or -CO-, the group represented by formula (b1-1) or formula (b1-3) is preferable.

[0092] Examples of the group represented by formula (b1-1) include the groups represented by formulas (b1-4) to (b1-8), respectively. TIFF0007704551000056.tif48120[In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, L b9 and Lb10 The total number of carbon atoms is 20 or less. In formula (b1-6), L b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. However, the total number of carbon atoms of 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 -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. However, the total number of carbon atoms of L b13 to L b15 is 19 or less. In formula (b1-8), L b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced 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 a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. However, the total number of carbon atoms of L b16 to L b18 is 19 or less.

[0093] L b8is 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 b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0094] Examples of the group represented by formula (b1-3) include the groups represented by formulas (b1-9) to (b1-11). TIFF0007704551000057.tif23140[In formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b20represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms, hydroxy groups or alkylcarbonyloxy groups. -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the 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 formula (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms, hydroxy groups or alkylcarbonyloxy groups. -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, L b21 , L b22 and L b23 have a total carbon number of 21 or less. In formula (b1-11), L b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b26represents 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. -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms contained in the alkylcarbonyloxy group may be substituted with hydroxy groups. However, L b24 , L b25 and L b26 have a total carbon number of 21 or less.

[0095] In the group represented by the formula (b1-9) to the group represented by the formula (b1-11), when the hydrogen atoms contained in the saturated hydrocarbon group are substituted with alkylcarbonyloxy groups, the carbon number before replacement is taken as the carbon number of the saturated hydrocarbon group.

[0096] Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group and the like.

[0097] Examples of the group represented by the formula (b1-4) include the following. TIFF0007704551000058.tif16154

[0098] Examples of the group represented by the formula (b1-5) include the following. TIFF0007704551000059.tif68152

[0099] Examples of the group represented by the formula (b1-6) include the following. TIFF0007704551000060.tif32164

[0100] Examples of the group represented by the formula (b1-7) include the following. TIFF0007704551000061.tif57146

[0101] Examples of the group represented by formula (b1-8) include the following. TIFF0007704551000062.tif23150

[0102] Examples of the group represented by formula (b1-2) include the following. TIFF0007704551000063.tif31161

[0103] Examples of the group represented by formula (b1-9) include the following. TIFF0007704551000064.tif44137

[0104] Examples of the group represented by formula (b1-10) include the following. TIFF0007704551000065.tif92165

[0105] Examples of the group represented by formula (b1-11) include the following. TIFF0007704551000066.tif84164

[0106] Examples of the alicyclic hydrocarbon group represented by Y include the groups represented by formula (Y1) to formula (Y11), formula (Y36) to formula (Y38). When -CH2- contained in the alicyclic hydrocarbon group represented by Y is replaced by -O-, -SO2- or -CO-, the number thereof may be one or two or more. Examples of such groups include the groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43). TIFF0007704551000067.tif84168

[0107] 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) to formula (Y40), formula (Y42) or formula (Y43), etc., the alkanediyl group between the two oxygen atoms preferably has one or more fluorine atoms. Further, among the alkanediyl groups contained in the ketal structure, it is preferable that the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom.

[0108] Examples of the substituent of the methyl group represented by Y include a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group, -(CH2) ja -CO-O-R b1 group or -(CH2) ja -O-CO-R b1 group (wherein R b1 represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or a group combining these. ja represents any integer from 0 to 4. The -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-, and the hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced by a hydroxy group or a fluorine atom.). etc. are mentioned. Examples of the substituent of the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 16 carbon atoms which may be substituted with a hydroxy group (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, a glycidyloxy group, -(CH2) ja -CO-O-R b1 group or -(CH2) ja -O-CO-R b1 group (wherein R b1 represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or a group combining these. ja represents any integer from 0 to 4. -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-, and a hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced by a hydroxy group or a fluorine atom.). etc. are mentioned.

[0109] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom etc. 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 etc. The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples include a methylcyclohexyl group, a dimethylcyclohexyl group etc. 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 phenyl group, naphthyl group, anthryl group, biphenyl group, and phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples of the aromatic hydrocarbon group having a chain hydrocarbon group with 1 to 18 carbon atoms include tolyl group, xylyl group, cumenyl group, mesityl group, p-methylphenyl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc., and examples of the aromatic hydrocarbon group having an alicyclic hydrocarbon group with 3 to 18 carbon atoms include p-cyclohexylphenyl group, 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 methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. Examples of the alkyl group substituted with a hydroxy group include hydroxyalkyl groups such as hydroxymethyl group and hydroxyethyl group. Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, and naphthylethyl group. Examples of the group in which -CH2- contained in the alkyl group is replaced with -O-, -SO2-, -CO-, etc. include alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, or a group combining these. 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. The number of carbon atoms of the alkoxy group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, and the like. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, a butyryl group, and the like. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, and the like. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the combined group include a group formed by combining an alkoxy group and an alkyl group, a group formed by combining an alkoxy group and an alkoxy group, a group formed by combining an alkoxy group and an alkylcarbonyl group, a group formed by combining an alkoxy group and an alkylcarbonyloxy group, and the like. Examples of the group formed by combining an alkoxy group and an alkyl group include alkoxyalkyl groups such as a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, an ethoxymethyl group, and the like. The number of carbon atoms in the alkoxyalkyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the group formed by combining an alkoxy group and an alkoxy group include alkoxyalkoxy groups such as a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, and the like. The number of carbon atoms in the alkoxyalkoxy group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the group formed by combining an alkoxy group and an alkylcarbonyl group include alkoxyalkylcarbonyl groups such as a methoxyacetyl group, a methoxypropionyl group, an ethoxyacetyl group, an ethoxypropionyl group, and the like. The number of carbon atoms in the alkoxyalkylcarbonyl group is preferably 3 to 13, more preferably 3 to 7, and still more preferably 3 to 5. Examples of the group combining an alkoxy group and an alkylcarbonyloxy group include alkoxyalkylcarbonyloxy groups such as methoxyacetyloxy group, methoxypropyonyloxy group, ethoxyacetyloxy group, and ethoxypropyonyloxy group. The number of carbon atoms in the alkoxyalkylcarbonyloxy group is preferably from 3 to 13, more preferably from 3 to 7, and even more preferably from 3 to 5. Examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -SO2- or -CO- etc. include the groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43).

[0110] Examples of Y include the following. TIFF0007704551000068.tif102165

[0111] TIFF0007704551000069.tif64161

[0112] 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, even more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, even more preferably an adamantyl group which may have a substituent, and -CH2- constituting the alicyclic hydrocarbon group or adamantyl group may be replaced by -CO-, -SO2- or -CO-. Specifically, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or the groups represented by formula (Y42), formula (Y100) to formula (Y114).

[0113] 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), and formula (B1-A-47) to formula (B1-A-59) is more preferable.

[0114] TIFF0007704551000070.tif87161

[0115] TIFF0007704551000071.tif122158

[0116] TIFF0007704551000072.tif100155

[0117] TIFF0007704551000073.tif64161

[0118] TIFF0007704551000074.tif112140

[0119] TIFF0007704551000075.tif87165

[0120] TIFF0007704551000076.tif99161 Here, R i2 ~R i7 are each independently, 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 1 and Q 2 represent the same meaning as described above. Examples of the anion represented by formula (I-A) specifically include the anions described in JP-A-2010-204646.

[0121] Examples of the anion in the preferably salt represented by formula (B1) include the anions respectively represented by formula (B1a-1) to formula (B1a-38). TIFF0007704551000077.tif209161

[0122] TIFF0007704551000078.tif168155

[0123] Among them, an anion represented by any of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-16), formula (B1a-18), formula (B1a-19), formula (B1a-22) to formula (B1a-38) is preferred.

[0124] 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 formula (b2-1) to formula (b2-4) (hereinafter may be referred to as "cation (b2-1)" etc. according to the formula number) are included. TIFF0007704551000079.tif45166In formula (b2-1) to formula (b2-4), R b4 ~R b6Each 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 atoms 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, and the hydrogen atoms 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 atoms contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. R b4 and R b5 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and -CH2- contained in the ring may be replaced with -O-, -S-, or -CO-. R b7 and R b8 each independently represents a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent any integer from 0 to 5. When m2 is 2 or more, a plurality of R b7 may be the same or different, and when n2 is 2 or more, a 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 -CH2- contained in the ring may be replaced with -O-, -S-, or -CO-. R b11 represents a hydrogen atom, a linear hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. Rb12 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 atoms contained in the chain hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms 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 may be bonded to each other to form a ring including -CH-CO- to which they are bonded, and -CH2- contained in the ring may be replaced with -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, 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, a plurality of R b13 are the same or different, when p2 is 2 or more, a plurality of R b14 are the same or different, when q2 is 2 or more, a plurality of R b15 are the same or different, when r2 is 2 or more, a plurality of R b16 are the same or different, when s2 is 2 or more, a plurality of R b17 are the same or different, when t2 is 2 or more, a 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 ~Rb12 The chain hydrocarbon group preferably has 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. TIFF0007704551000080.tif10159 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 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 and having a fluorine atom, and examples 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, biphenylyl group, naphthyl group, and phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples of the aromatic hydrocarbon group having a chain hydrocarbon group with 1 to 18 carbon atoms include (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 examples of the aromatic hydrocarbon group having an alicyclic hydrocarbon group with 3 to 18 carbon atoms include (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, etc. 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, etc. Examples of the alkylcarbonyl group include acetyl group, propionyl group, and butyryl group, etc. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom, etc. 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, etc. 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. TIFF0007704551000081.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.

[0125] Among cations (b2-1) to (b2-4), preferably, it is cation (b2-1). Examples of cation (b2-1) include the following cations. TIFF0007704551000082.tif73149

[0126] TIFF0007704551000083.tif110165

[0127] Examples of cation (b2-2) include the following cations and the like. TIFF0007704551000084.tif18150

[0128] Examples of the cation (b2-3) include the following cations and the like. TIFF0007704551000085.tif24126

[0129] Examples of the cation (b2-4) include the following cations and the like. TIFF0007704551000086.tif127165

[0130] 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, 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 a combination with the cation (b2-1), the cation (b2-3), or the cation (b2-4) are mentioned.

[0131] 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. TIFF0007704551000087.tif87150

[0132] TIFF0007704551000088.tif145158

[0133] TIFF0007704551000089.tif92153

[0134] TIFF0007704551000090.tif127143 JPEG0007704551000091.jpg62163

[0135] TIFF0007704551000092.tif92158

[0136] 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, and still more preferably 3 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the resin (A). The resist composition of the present invention may contain one kind of the acid generator (B) alone or a plurality of kinds.

[0137] <Resin (A)> The resin (A) has a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)"). The resin (A) preferably further contains a structural unit other than the structural unit (a1). Examples of the structural unit other than the structural unit (a1) include a structural unit having no acid-labile group (hereinafter sometimes referred to as "structural unit (s)"), a structural unit other than the structural unit (a1) and the structural unit (s) (for example, a structural unit having a halogen atom described later (hereinafter sometimes referred to as "structural unit (a4)"), a structural unit having a non-leaving hydrocarbon group described later (hereinafter sometimes referred to as "structural unit (a5)"), and other structural units derived from monomers known in the art).

[0138] 〈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)"). TIFF0007704551000093.tif2397[In 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 a2are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bonding position. TIFF0007704551000094.tif2379[In formula (2), R a1’ and R a2’ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and 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 atoms to which they are bonded and X, and -CH2- contained in the hydrocarbon group and the heterocyclic group may be replaced by -O- or -S-. X represents an oxygen atom or a sulfur atom. na’ represents 0 or 1. * represents a bond.

[0139] R a1 R a2 and R a3 Examples of the alkyl group in R 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. R a1 R a2 and R a3The alicyclic hydrocarbon group in [the formula] 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, etc. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups (* represents a bond). R a1 、R a2 and R a3 The number of carbon atoms of the alicyclic hydrocarbon group of R TIFF0007704551000095.tif10159R a1 、R a2 and R a3 Examples of the aromatic hydrocarbon group in [the formula] include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group, etc. Examples of the combined groups include groups 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 a1 and R a2 and R a3 are bonded to each other to form an alicyclic hydrocarbon group, examples of -C(R a1 )(R a2 )(R a3 ) include the following groups. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * represents the bonding position with -O-. TIFF0007704551000096.tif31135

[0140] R a1’ 、R a2’ and R a3’Examples of the hydrocarbon group in [description] include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these groups. The alkyl group and the alicyclic hydrocarbon group are R a1 , R a2 and R a3 include the same groups as those listed for R. 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. Examples of the combined group include a group formed by combining the above-described alkyl group and alicyclic hydrocarbon group (for example, an alkylcycloalkyl group or a cycloalkylalkyl group), an aralkyl group (such as a benzyl group), an aromatic hydrocarbon group having an alkyl group (a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (a p-cyclohexylphenyl group, a p-adamantylphenyl group, etc.), an alicyclic hydrocarbon group having an aromatic hydrocarbon group (a phenylcyclohexyl group, etc.). R a2’ and R a3’ When R and R are bonded to each other to form a heterocyclic group together with the carbon atom to which they are bonded and X, examples of -C(R a1’ )(R a2’ )-X-R a3’ include the following groups. * represents the bonding position. TIFF0007704551000097.tif21142R a1’ and R a2’ Among them, at least one of them is preferably a hydrogen atom. na' is preferably 0.

[0141] Examples of the group (1) include the following groups. In formula (1), when R a1 , R a2 and R a3 are alkyl groups, ma = 0, and na = 1. As the 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 group. 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 group. Specific examples of the group (1) include the following groups. * represents a bond. TIFF0007704551000098.tif171163

[0142] Specific examples of the group (2) include the following groups. * represents a bonding position. TIFF0007704551000099.tif74154

[0143] The monomer (a1) is preferably a monomer having an acid-labile group and an ethylenically unsaturated bond, more preferably a (meth)acrylic monomer having an acid-labile group.

[0144] Among the (meth)acrylic monomers having an acid-labile group, preferably those having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are 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 the resist composition, the resolution of the resist pattern can be improved.

[0145] As a structural unit derived from a (meth)acrylic monomer having a group (1), there are a structural unit represented by formula (a1-0) (hereinafter sometimes referred to as structural unit (a1-0)), a structural unit represented by formula (a1-1) (hereinafter sometimes referred to as structural unit (a1-1)), or a structural unit represented by formula (a1-2) (hereinafter sometimes referred to as structural unit (a1-2)). Preferably, it is at least one structural unit selected from the group consisting of structural unit (a1-1) and structural unit (a1-2). These may be used alone or in combination of two or more. TIFF0007704551000100.tif42141[In formula (a1-0), formula (a1-1), and formula (a1-2), L a01 、L a1 and L a2 each independently represents -O- or * -O-(CH2) k1 -CO-O-, k1 represents an integer of 1 to 7, and * represents a bond to -CO-. R a01 、R a4 and R a5 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a02 、R a03 and R a04 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1’ represents an integer of 0 to 3.]

[0146] R a01 、Ra4 and R a5 is preferably a hydrogen atom or a methyl group, more preferably a methyl group. L a01 、L a1 and L a2 is preferably an oxygen atom or *-O-(CH2) k01 -CO-O- (wherein k01 is preferably any integer from 1 to 4, more preferably 1). More preferably, it is an oxygen atom. R a02 、R a03 and R a04 Examples of the alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and combinations thereof in R a1 ~R a3 are the same groups as those listed for the groups in formula (1). R a6 and R a7 Examples of the alkyl group, alkenyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and combinations thereof in R a1 、R a2 and R a3 are the same groups as those listed for the groups in formula (1). R a02 、R a03 、and R a04 The alkyl group in R R a6 and R a7 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R a6 and R a7 The alkyl group in R R a02 、R a03 and R a04The number of carbon atoms of the alicyclic hydrocarbon group is preferably 5 to 12, more preferably 5 to 10. R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms of the aromatic hydrocarbon group of R For the group combining an alkyl group and an alicyclic hydrocarbon group, the total number of carbon atoms of these alkyl group and alicyclic hydrocarbon group combined is preferably 18 or less. For the group combining an alkyl group and an aromatic hydrocarbon group, the total number of carbon atoms of these alkyl group and aromatic hydrocarbon group combined is preferably 18 or less. R a02 and R a03 are preferably an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a phenyl group or a naphthyl group. R a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. R a6 and R a7 are preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group, a phenyl group or a naphthyl group, still more preferably an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group or a phenyl group. m1 is preferably any integer from 0 to 3, more preferably 0 or 1. n1 is preferably any integer from 0 to 3, more preferably 0 or 1. n1' is preferably 0 or 1.

[0147] As the structural unit (a1-0), for example, the structural unit represented by any of Formula (a1-0-1) to Formula (a1-0-18) and R in the structural unit (a1-0)a01 Examples of the structural unit in which the methyl group corresponding to [ID] is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group include structural units represented by any of formula (a1-0-1) to formula (a1-0-10), formula (a1-0-13), and formula (a1-0-14), and a structural unit represented by any of these is preferred. TIFF0007704551000101.tif99168

[0148] Examples of the structural unit (a1-1) include structural units derived from the monomers described in JP-A-2010-204646. Among them, the structural units represented by any of formula (a1-1-1) to formula (a1-1-7) and R in the structural unit (a1-1) a4 A structural unit in which the methyl group corresponding to [ID] is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group is preferred, and a structural unit represented by any of formula (a1-1-1) to formula (a1-1-4) is more preferred. TIFF0007704551000102.tif38168

[0149] Examples of the structural unit (a1-2) include structural units represented by any of formula (a1-2-1) to formula (a1-2-12) and R in the structural unit (a1-2) a5 Examples of the structural unit in which the methyl group corresponding to [ID] is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group include structural units represented by any of formula (a1-2-2), formula (a1-2-5), formula (a1-2-6), and formula (a1-2-10) to formula (a1-2-12), and a structural unit represented by any of these is preferred. TIFF0007704551000103.tif74155

[0150] When the resin (A) contains the structural unit (a1-0), its content is usually 5 to 60 mol%, preferably 5 to 50 mol%, and more preferably 10 to 40 mol% based on all the structural units of the resin (A). When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is usually 10 to 95 mol%, preferably 15 to 85 mol%, more preferably 15 to 80 mol%, still more preferably 20 to 80 mol%, and even more preferably 20 to 75 mol% based on all the structural units of the resin (A).

[0151] 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)"). TIFF0007704551000104.tif3854[In the formula (a1-4), R a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a33 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. A a30 represents a single bond or * -X a31 -(A a32 -X a32 ) nc - and * represents the bonding site with the carbon atom to which -R a32 is bonded. A a32 represents an alkanediyl group having 1 to 6 carbon atoms. X a31 and X a32 each independently represents -O-, -CO-O- or -O-CO-. nc represents 0 or 1. la represents any integer from 0 to 4. When la is any integer of 2 or more, a plurality of R a33 may be the same as or different from each other. R a34 and R a35each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R a36 are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -C-O- to which they are bonded, and -CH2- contained in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-.

[0152] R a32 and R a33 Examples of the halogen atom in R and R include a fluorine atom, a chlorine atom, and a bromine atom. R a32 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, and a perfluorohexyl group. R 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 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. R a33 Examples of the alkoxy group in R include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, 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. Ra33 Examples of the alkoxyalkyl group in [reference to something not specified] include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group. R a33 Examples of the alkoxyalkoxy group in [reference to something not specified] include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethyl group or an ethoxyethyl group. R a33 Examples of the alkylcarbonyl group in [reference to something not specified] include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group. R a33 Examples of the alkylcarbonyloxy group in [reference to something not specified] include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group. R a33 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group, and even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0153] *-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- is included. Among them, *-CO-O-, *-CO-O-A a32 -CO-O- or *-O-A a32 -CO-O- is preferred.

[0154] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. A a32 is preferably a methylene group or an ethylene group.

[0155] A a30 is preferably a single bond, *-CO-O- or *-CO-O-A a32 -CO-O-, more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferably a single bond or *-CO-O-.

[0156] la is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0. R a34 、R a35 and R a36 Examples of the hydrocarbon group in include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group combining these. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, etc. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* represents the bonding site). TIFF0007704551000105.tif10151Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group and the like. Examples of the combined group include a group formed by combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, cycloalkylalkyl group), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group and the like. In particular, R a36 Examples of R include an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these.

[0157] R a34 is preferably a hydrogen atom. R a35 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a methyl group or an ethyl group. R a36 The hydrocarbon group of R is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these, and more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. R a36The alkyl group and 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.

[0158] -OC(R a34 )(R a35 )-O-R a36 in the structural unit (a1-4) eliminates upon contact with an acid (e.g., p-toluenesulfonic acid) to form a hydroxy group. -OC(R a34 )(R a35 )-O-R a36 is preferably bonded to the o-position or p-position of the benzene ring, more preferably to the p-position.

[0159] 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 hydrogen atom corresponding to R a32 in the structural unit (a1-4) are replaced with a halogen atom, a haloalkyl group or an alkyl group, 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), formula (a1-4-14) are mentioned. When the resin (A) has the structural unit (a1-4), its content is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, and even more preferably 10 to 40 mol% based on the total of all the structural units of the resin (A).

[0160] Examples of the structural unit derived from the (meth)acrylic monomer having the group (2) also include the structural unit represented by formula (a1-5) (hereinafter sometimes referred to as "structural unit (a1-5)"). TIFF0007704551000107.tif4354In formula (a1-5), R a8represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. Z a1 is a single bond or *-(CH2) h3 -CO-L 54 -, h3 represents an integer of any one of 1 to 4, and * represents the bonding position with 51 L. L 51 L 52 L 53 and L 54 each independently represents -O- or -S-. s1 represents an integer of any one of 1 to 3. s1’ represents an integer of any one of 0 to 3.

[0161] Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is preferred. Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluoromethyl group and a trifluoromethyl group. In formula (a1-5), R a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group. L 51 is preferably an oxygen atom. L 52 and L 53 Among them, it is preferable that one is -O- and the other is -S-. s1 is preferably 1. s1’ is preferably an integer of any one of 0 to 2. Z a1 is preferably a single bond or *-CH2-CO-O-.

[0162] Examples of the structural unit (a1-5) include structural units derived from monomers described in JP-A-2010-61117. Among them, the structural units represented by formula (a1-5-1) to formula (a1-5-4) are preferable, and the structural unit represented by formula (a1-5-1) or formula (a1-5-2) is more preferable. When the resin (A) has the structural unit (a1-5), its content is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, still more preferably 5 to 40 mol%, and even more preferably 5 to 30 mol% based on all the structural units of the resin (A).

[0163] Examples of the structural unit (a1) also include the following structural units. When the resin (A) contains the above structural unit, its content is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, and still more preferably 10 to 40 mol% based on all the structural units of the resin (A).

[0164] 〈Structural unit (s)〉 The structural unit (s) is derived from a monomer having no acid-labile group (hereinafter sometimes referred to as "monomer (s)"). As the monomer for deriving the structural unit (s), a monomer having no acid-labile group known in the resist field can be used. The structural unit (s) preferably has a hydroxy group or a lactone ring. By using a resin having a structural unit having a hydroxy group and no acid-labile group (hereinafter sometimes referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and no acid-labile group (hereinafter sometimes referred to as "structural unit (a3)") in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

[0165] 〈Structural unit (a2)〉 The hydroxy group of the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. When producing a resist pattern from the resist composition of the present invention, when using a high-energy ray such as a KrF excimer laser (248 nm), an electron beam, or EUV (extreme ultraviolet light) as an exposure light source, as the structural unit (a2), a structural unit (a2) having a phenolic hydroxy group is preferable, and it is more preferable to use the structural unit (a2-A) described later. When using an ArF excimer laser (193 nm) or the like, as the structural unit (a2), a structural unit (a2) having an alcoholic hydroxy group is preferable, and it is more preferable to use the structural unit (a2-1) described later. The structural unit (a2) may be contained alone as one kind or may contain two or more kinds.

[0166] 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)"). TIFF0007704551000110.tif4348[In the formula (a2-A), R a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a50 represents a single bond or *-X a51 -(A a52 -X a52 ) nb -, where * represents the bonding position with the carbon atom to which -R a50 is bonded. A a52 each independently represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O-, or -O-CO-. nb represents 0 or 1. mb represents any integer from 0 to 4. When mb is any integer of 2 or more, a plurality of R a51 may be the same as or different from each other.]

[0167] R a50 and R a51 Examples of the halogen atom in R R a50 The alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R R a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a51 Examples of the alkyl group in R R a51 Examples of the alkoxy group in R R a51Examples of the alkoxyalkyl group herein include methoxymethyl group, ethoxyethyl group, propoxymethyl group, isopropoxymethyl group, butoxymethyl group, sec-butoxymethyl group, and tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group. R a51 Examples of the alkoxyalkoxy group herein include methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, ethoxyethoxy group, propoxymethoxy group, isopropoxymethoxy group, butoxymethoxy group, sec-butoxymethoxy group, and tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethoxy group or an ethoxyethoxy group. R a51 Examples of the alkylcarbonyl group herein include acetyl group, propionyl group, and butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group. R a51 Examples of the alkylcarbonyloxy group herein include acetyloxy group, propionyloxy group, and butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and 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.

[0168] *-X a51 -(A a52 -X a52 ) nb- 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- is included. Among them, *-CO-O-, *-CO-O-A a52 -CO-O- or *-O-A a52 -CO-O- is preferred. Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. A a52 is preferably a methylene group or an ethylene group. A a50 is a single bond, *-CO-O- or *-CO-O-A a52 -CO-O- is preferred, more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferably a single bond or *-CO-O-. mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0. The hydroxy group is preferably bonded to the ortho position or the para position of the benzene ring, and more preferably bonded to the para position.

[0169] Examples of the structural unit (a2-A) include structural units derived from monomers described in JP-A-2010-204634 and JP-A-2012-12577. Examples of the structural unit (a2-A) include structural units represented by formula (a2-2-1) to formula (a2-2-16), and R in the structural unit (a2-A) in the structural units represented by formula (a2-2-1) to formula (a2-2-16). a50Examples of the structural unit include those in which the methyl group corresponding to [[ID=]] is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group. The structural unit (a2-A) is the structural unit represented by formula (a2-2-1), the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-6), the structural unit represented by formula (a2-2-8), the structural units represented by formulas (a2-2-12) to (a2-2-14), and in the structural unit represented by formula (a2-2-1), the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-6), the structural unit represented by formula (a2-2-8), the structural units represented by formulas (a2-2-12) to (a2-2-14), R in the structural unit (a2-A) a50 is preferably a structural unit in which the methyl group corresponding to [[ID=]] is replaced with a hydrogen atom, and in the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-8), the structural units represented by formulas (a2-2-12) to (a2-2-14), and the structural unit represented by formula (a2-2-3) or the structural unit represented by formula (a2-2-8), the structural units represented by formulas (a2-2-12) to (a2-2-14), R in the structural unit (a2-A) a50 is more preferably a structural unit in which the methyl group corresponding to [[ID=]] is replaced with a hydrogen atom, and in the structural unit represented by formula (a2-2-8) and the structural unit represented by formula (a2-2-8), R in the structural unit (a2-A) a50 is even more preferably a structural unit in which the methyl group corresponding to [[ID=]] is replaced with a hydrogen atom. When the structural unit (a2-A) is contained in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, even more preferably 15 to 65 mol%, and even more preferably 20 to 65 mol% with respect to all the structural units. The structural unit (a2-A) can be incorporated into the resin (A) by, for example, polymerizing using the structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. Also, after polymerizing using acetoxystyrene or the like, the structural unit (a2-A) can be incorporated into the resin (A) by treating with an alkali such as tetramethylammonium hydroxide.

[0170] Examples of the structural unit having an alcoholic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)"). In the formula (a2-1) in TIFF0007704551000112.tif4261, L a3 represents -O- or * -O-(CH2) k2 -CO-O-, k2 represents an integer of any one of 1 to 7. * represents the bonding position with -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 each independently represent a hydrogen atom, a methyl group or a hydroxy group. o1 represents an integer of any one of 0 to 10.

[0171] In the formula (a2-1), L a3 is preferably -O-, -O-(CH2) f1 -CO-O- (wherein f1 represents an integer of any one of 1 to 4), more preferably -O-. R a14 is preferably a methyl group. R a15 is preferably a hydrogen atom. R a16 is preferably a hydrogen atom or a hydroxy group. o1 is preferably an integer of any one of 0 to 3, more preferably 0 or 1.

[0172] Examples of the structural unit (a2-1) include structural units derived from monomers described in JP 2010-204646 A. A structural unit represented by any one of formulas (a2-1-1) to (a2-1-6) is preferred, a structural unit represented by any one of formulas (a2-1-1) to (a2-1-4) is more preferred, and a structural unit represented by formula (a2-1-1) or formula (a2-1-3) is even more preferred. TIFF0007704551000113.tif54149 When resin (A) contains the structural unit (a2-1), the content thereof is usually 1 to 45 mol %, preferably 1 to 40 mol %, more preferably 1 to 35 mol %, even more preferably 2 to 20 mol %, and still more preferably 2 to 10 mol %, based on all structural units of resin (A).

[0173] <Structural unit (a3)> The lactone ring of the structural unit (a3) ​​may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring, or a δ-valerolactone ring, or may be a condensed ring of a monocyclic lactone ring and another ring. Preferred examples include a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)). The structural unit (a3) ​​is preferably a structural unit represented by formula (a3-1), (a3-2), (a3-3) or (a3-4). One of these may be contained alone, or two or more of them may be contained. TIFF0007704551000114.tif51161 [In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4), L a4 , L a5 and L a6 are each independently -O- or *-O-(CH2) k3 It represents a group represented by -CO-O- (k3 represents an integer of any of 1 to 7). L a7 , -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -CO-OLa9 -CO-O- or *-O-L a8 -O-CO-L a9 -O- represents. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * represents the bonding site with the carbonyl group. R a18 R a19 and R a20 each independently represents a hydrogen atom or a methyl group. R a24 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. X a3 represents -CH2- or an oxygen atom. R a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R a22 R a23 and R a25 each independently represents a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. p1 represents any integer from 0 to 5. q1 represents any integer from 0 to 3. r1 represents any integer from 0 to 3. w1 represents any integer from 0 to 8. When p1, q1, r1 and / or w1 is 2 or more, a plurality of R a21 R a22 R a23 and / or R a25 may be the same as or different from each other.

[0174] R a21 R a22 R a23 and R a25 Examples of the aliphatic hydrocarbon group in R R a24Examples of the halogen atom in [the compound] include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R a24 Examples of the alkyl group in [the compound] 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, etc. Preferably, an alkyl group having 1 to 4 carbon atoms is exemplified, and more preferably, a methyl group or an ethyl group is exemplified. R a24 Examples of the alkyl group having a halogen atom in [the compound] include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, etc.

[0175] L a8 and L a9 Examples of the alkanediyl group in [the compound] and [the other compound] include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group, etc.

[0176] In formulas (a3-1) to (a3-3), L a4 ~L a6 are each independently preferably -O- or, *-O-(CH2) k3 -CO-O- in which k3 is an integer of 1 to 4, more preferably -O- and, *-O-CH2-CO-O-, and even more preferably an oxygen atom. R a18 ~R a21 is preferably a methyl group. R a22 and R a23 are each independently preferably a carboxy group, a cyano group, or a methyl group. p1, q1, and r1 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

[0177] In formula (a3-4), R a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a25 is preferably a carboxy group, a cyano group, or a methyl group. L a7 is preferably -O- or *-O-L a8 -CO-O-, more preferably -O-, -O-CH2-CO-O-, or -O-C2H4-CO-O-. w1 is preferably an integer of 0 to 2, more preferably 0 or 1. In particular, formula (a3-4) is preferably formula (a3-4)'. TIFF0007704551000115.tif4051 (wherein R a24 , L a7 represents the same meaning as described above.)

[0178] 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. When the resin (A) contains the structural unit (a3), the total content is usually 1 to 70 mol%, preferably 1 to 65 mol%, more preferably 1 to 60 mol% based on all the structural units of the resin (A). In addition, the content of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit (a3-4) is preferably 1 to 60 mol%, more preferably 1 to 50 mol%, still more preferably 1 to 50 mol% based on all the structural units of the resin (A).

[0179] 〈Structural unit (a4)〉 Examples of the structural unit (a4) include the following structural units. TIFF0007704551000117.tif3165[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having 1 to 24 carbon atoms and a fluorine atom, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-.] R 42 Examples of the saturated hydrocarbon group represented by include a chain hydrocarbon group, a monocyclic or polycyclic alicyclic hydrocarbon group, and a group formed by combining these.

[0180] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group. Examples of the monocyclic or polycyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents the bonding position). As the group formed by the combination of 11160 combinations of TIFF0007704551000118.tif, groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups can be mentioned, such as -alkanediyl group - alicyclic hydrocarbon group, -alicyclic hydrocarbon group - alkyl group, -alkanediyl group - alicyclic hydrocarbon group - alkyl group, etc.

[0181] Examples of the structural unit (a4) include structural units represented by at least one selected from the group consisting of formula (a4-0), formula (a4-1), formula (a4-2), formula (a4-3) and formula (a4-4). TIFF0007704551000119.tif3953[In formula (a4-0), R 5a represents a hydrogen atom or a methyl group. L 4a represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3a represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms. R 6a represents a hydrogen atom or a fluorine atom.]

[0182] L 4a Examples of the alkanediyl group in include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, and branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group.

[0183] L 3aExamples of the perfluoroalkanediyl group in [the compound] 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 [the compound] include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, a perfluoroadamantanediyl group, and the like.

[0184] L 4a is preferably a single bond, a methylene group, or an ethylene group, and more preferably a single bond or a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0185] Examples of the structural unit (a4-0) include the following structural units and structural units in which the methyl group corresponding to R in the following structural units is replaced by a hydrogen atom in the structural unit (a4-0). 5a TIFF0007704551000120.tif95165

[0186] ​ TIFF0007704551000121.tif5170[In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. A a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by formula (a-g1). However, A a41 and R a42 at least one of which has a halogen atom (preferably a fluorine atom) as a substituent. TIFF0007704551000122.tif1383[In formula (a-g1), s represents 0 or 1. A a42 and A a44 each independently represent a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. A a43 represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. X a41 and X a42 each independently represent -O-, -CO-, -CO-O- or -O-CO-. However, the total number of carbon atoms of A a42 , A a43 , A a44 , X a41 and X a42 is 7 or less. ] * represents a bonding position, and the * on the right side is the bonding position with -O-CO-R a42 . ]

[0187] 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.

[0188] Examples of the chain saturated hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group. Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; polycyclic alicyclic saturated hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group, and the following group (* represents the bonding position). Examples of the group formed by the combination of TIFF0007704551000123.tif11160 include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic saturated hydrocarbon groups, such as -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group, and the like.

[0189] R a42 Examples of the substituent that R has include at least one selected from the group consisting of a halogen atom and a group represented by the formula (a-g3). Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom, and preferably a fluorine atom. TIFF0007704551000124.tif752 [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. * is the bonding position 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 and having at least one halogen atom.

[0190] A a45 Examples of the aliphatic hydrocarbon group in include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl; monocyclic alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, norbornyl, and the following group (* represents the bonding position). TIFF0007704551000125.tif11160

[0191] R a42 R is preferably a saturated hydrocarbon group which may have a halogen atom, more preferably an alkyl group having a halogen atom and / or a saturated hydrocarbon group having a group represented by the formula (a-g3). R a42 When R is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, still more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the perfluoroalkyl group include perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, and perfluorooctyl. Examples of the perfluorocycloalkyl group include perfluorocyclohexyl. R a42 When R is a saturated hydrocarbon group having a group represented by the formula (a-g3), including the carbon atoms contained in the group represented by the formula (a-g3), the total carbon number of R a42 is preferably 15 or less, more preferably 12 or less. When having a group represented by the formula (a-g3) as a substituent, the number thereof is preferably 1.

[0192] R a42 When R is a saturated hydrocarbon group having a group represented by formula (a-g3), a42 it is more preferably a group represented by formula (a-g2). TIFF0007704551000126.tif874[In formula (a-g2), A a46 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. X a44 represents **-O-CO- or **-CO-O- (** represents the bonding position with 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 the bonding position with the carbonyl group.]

[0193] A a46 The number of carbon atoms of the saturated 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.

[0194] The preferred structure of the group represented by formula (a-g2) is the following structure (* is the bonding position with the carbonyl group). TIFF0007704551000127.tif13161

[0195] A a41Examples 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 represented by the formula (I) 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.

[0196] A in the group represented by formula (a-g1) a42 , A a43 and A a44 Examples of the divalent saturated hydrocarbon group represented by include linear or branched alkanediyl groups, monocyclic or polycyclic divalent alicyclic hydrocarbon groups, and groups formed by combining alkanediyl groups and divalent alicyclic hydrocarbon groups, 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.

[0197] In the group represented by formula (a-g1), X a42 Examples of the group in which is -O-, -CO-, -CO-O-, or -O-CO- include the following groups. In the following examples, * and ** each represent a bond position, and ** represents -O-CO-Ra42 is a bonding site with TIFF0007704551000128.tif48153

[0198] Examples of the structural unit represented by the formula (a4-1) include the following structural units and the structural units represented by the formula (a4-1) in the following structural units, where the methyl group corresponding to R a41 is replaced by a hydrogen atom. TIFF0007704551000129.tif102149 TIFF0007704551000130.tif123141

[0199] As the structural unit represented by the formula (a4-1), the structural unit represented by the formula (a4-2) is preferred. TIFF0007704551000131.tif3962[In the formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 represents an alkanediyl group having 1 to 6 carbon atoms, and -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-. R f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms and having a fluorine atom. However, the upper limit of the total number of carbon atoms of L 44 and R f6 is 21.]

[0200] Examples of the alkanediyl group of L 44 include the same groups as those exemplified by A a41 . Examples of the saturated hydrocarbon group of R f6 include the same groups as those exemplified by R a42 . As the alkanediyl group in L 44 , an alkanediyl group having 2 to 4 carbon atoms is preferred, and an ethylene group is more preferred.

[0201] Examples of the structural unit represented by formula (a4-2) include structural units represented by formulas (a4-1-1) to (a4-1-11), respectively. In the structural unit (a4-2), the methyl group corresponding to R f5 replaced by a hydrogen atom is also included as a structural unit represented by formula (a4-2).

[0202] TIFF0007704551000132.tif5468[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 represents an alkanediyl group having 1 to 6 carbon atoms. A f13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom. X f12 represents *-O-CO- or *-CO-O- (* represents the bonding position to 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.]

[0203] Examples of the alkanediyl group in L 5 include the same groups as those exemplified for the alkanediyl group in A a41 . A f13 The divalent saturated hydrocarbon group which may have a fluorine atom in preferably includes a divalent chain saturated hydrocarbon group which may have a fluorine atom and a divalent alicyclic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group. Examples of the divalent chain hydrocarbon group which may have a fluorine atom include alkane diyl groups such as methylene group, ethylene group, propane diyl group, butane diyl group and pentane diyl group; perfluoroalkane diyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropane diyl group, perfluorobutane diyl group and perfluoropentane diyl group, and the like. The divalent alicyclic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic group include cyclohexane diyl group and perfluorocyclohexane diyl group. Examples of the polycyclic group include adamantane diyl group, norbornane diyl group, perfluoroadamantane diyl group, and the like.

[0204] A f14 Examples of the saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom of a42 are the same groups as those exemplified by R. Among them, 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 and the like are preferable.

[0205] In formula (a4-3), L 5 is preferably an ethylene group. A f13The divalent saturated hydrocarbon group preferably includes a divalent chain hydrocarbon group having 1 to 6 carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a divalent chain hydrocarbon group having 2 to 3 carbon atoms. A f14 The saturated hydrocarbon group preferably includes a chain hydrocarbon group having 3 to 12 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a group including a chain hydrocarbon group having 3 to 10 carbon atoms and an alicyclic hydrocarbon group having 3 to 10 carbon atoms. Among them, A f14 is preferably a group including an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

[0206] Examples of the structural unit represented by formula (a4-3) include structural units respectively represented by formulas (a4-1'-1) to (a4-1'-11). The methyl group corresponding to R f7 in the structural unit (a4-3) replaced by a hydrogen atom is also included as a structural unit represented by formula (a4-3).

[0207] Examples of the structural unit (a4) also include a structural unit represented by formula (a4-4). TIFF0007704551000133.tif4162[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 represents -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 -, or -(CH2) j4 -CO-O-(CH2) j5 -. j1 to j5 each independently represent an integer of 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom.

[0208] R f22 The saturated hydrocarbon group of R a42Examples thereof include the same as the saturated hydrocarbon group represented by R f22 is preferably an alkyl group having 1 to 10 carbon atoms or an alicyclic hydrocarbon group having 1 to 10 carbon atoms, each having a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom, and still more preferably an alkyl group having 1 to 6 carbon atoms having a fluorine atom. In formula (a4-4), A f21 is preferably -(CH2) j1 -, more preferably an ethylene group or a methylene group, and still more preferably a methylene group.

[0209] Examples of the structural unit represented by formula (a4-4) include the following structural units and the structural units represented by the following formulas, in which the methyl group corresponding to R in structural unit (a4-4) is replaced by a hydrogen atom. f21 are mentioned. When the resin (A) has the structural unit (a4), its content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and still more preferably 3 to 10 mol% based on all the structural units of the resin (A).

[0210] 〈Structural unit (a5)〉 Examples of the non-leaving hydrocarbon group in the structural unit (a5) include groups 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). TIFF0007704551000135.tif3972[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atoms contained in the alicyclic hydrocarbon group may be substituted with aliphatic hydrocarbon groups having 1 to 8 carbon atoms. L 55represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-.

[0211] R 52 The alicyclic hydrocarbon group in 52 may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, and a 2-ethylhexyl group. Examples of the alicyclic hydrocarbon group having a substituent include a 3-methyladamantyl group. R 52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, more preferably an adamantyl group, a norbornyl group, or a cyclohexyl group.

[0212] L 55 Examples of the divalent saturated hydrocarbon group in 55 include a divalent chain saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and preferably a divalent chain saturated hydrocarbon group. Examples of the divalent chain saturated hydrocarbon group include alkanediyl groups such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group, and a pentanediyl group. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include cycloalkanediyl groups such as a cyclopentanediyl group and a cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantanediyl group and a norbornanediyl group.

[0213] L 55Examples of the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced by -O- or -CO- include groups represented by formula (L1-1) to formula (L1-4). In the following formulas, * and ** represent bonding positions, and * represents the bonding position with an oxygen atom. In formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents the bonding position with L x1 .). L x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, the total number of carbon atoms of L x1 and L x2 is 16 or less. In formula (L1-2), L x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms. L x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, the total number of carbon atoms of L x3 and L x4 is 17 or less. In formula (L1-3), L x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. L x6 and L x7 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms. However, the total number of carbon atoms of L x5 , L x6 and L x7 is 15 or less. In formula (L1-4), L x8 and L x9 each represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms. However, L x8 , L x9 and W x1 have a total carbon number of 15 or less.

[0214] 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.

[0215] Examples of the group represented by the formula (L1-1) include the following divalent groups. TIFF0007704551000137.tif54134

[0216] Examples of the group represented by formula (L1-2) include the following divalent groups. TIFF0007704551000138.tif24131

[0217] Examples of the group represented by formula (L1-3) include the following divalent groups. TIFF0007704551000139.tif15162

[0218] Examples of the group represented by formula (L1-4) include the following divalent groups. TIFF0007704551000140.tif26114L 55 is preferably a single bond or a group represented by formula (L1-1).

[0219] Examples of the structural unit (a5-1) include the following structural units and the structural units (a5-1) in the following structural units where the methyl group corresponding to R 51 is replaced by a hydrogen atom. TIFF0007704551000141.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).

[0220] <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.

[0221] 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 the formula (II-2-A’). TIFF0007704551000142.tif36104[In the formula (II-2-A’), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-, and a hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom or a hydroxy group. A x1 represents an alkanediyl group having 1 to 8 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be replaced 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.]

[0222] R III3 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom and 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 x1Examples of the C1-C8 alkanediyl group represented by include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, and the like. A x1 Examples of the C1-C6 perfluoroalkyl group which may be substituted at include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, a perfluorohexyl group, and the like. X III3 Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and combinations thereof. Specifically, linear alkanediyl groups such as 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 heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group; branched alkanediyl groups such as 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; 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; and divalent polycyclic alicyclic saturated hydrocarbon groups 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, and the like. Examples of the case where -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- include divalent groups represented by formula (X1) to formula (X53). However, the number of carbon atoms before -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- is 17 or less, respectively. In the following formula, * represents a bond to A x1 represents a bond to A TIFF0007704551000143.tif145161

[0223] 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

[0224] ZA in formula (II-2-A') + is the same as the cation Z1 in the acid generator (B1) + and the like can be mentioned

[0225] The structural unit represented by formula (II-2-A') is preferably the structural unit represented by formula (II-2-A). TIFF0007704551000144.tif38109[In formula (II-2-A), R III3 、X III3 and ZA + represent the same meaning as above z2A represents any integer from 0 to 6 R III2 and R III4Each independently represents 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 represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.] R III2 、R III4 、Q a and Q b Examples of the perfluoroalkyl group having 1 to 6 carbon atoms represented by R b1 、Q

[0226] The structural unit represented by the formula (II-2-A) is preferably the structural unit represented by the formula (II-2-A-1). TIFF0007704551000145.tif5578[In the 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, in which -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S-, or -CO-, and a hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom or a hydroxy group.] R III5Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by 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 include the same groups as those of the divalent saturated hydrocarbon group represented by X III3 .

[0227] As the structural unit represented by the formula (II-2-A-1), the structural unit represented by the formula (II-2-A-2) is more preferable. TIFF0007704551000146.tif5288[In the formula (II-2-A-2), R III3 and R III5 and ZA + have the same meanings as described above. mA and nA each independently represent 1 or 2.]

[0228] Examples of the structural unit represented by the formula (II-2-A') include, for example, the following structural units, a group corresponding to the methyl group of R III3 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 WO2012 / 050015. ZA + represents an organic cation. TIFF0007704551000147.tif86163

[0229] The structural unit having a sulfonio group and an organic anion in the side chain is preferably the structural unit represented by the formula (II-1-1). TIFF0007704551000148.tif3791[In the formula (II-1-1), A II1 represents a single bond or a divalent linking group. R II1represents 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 be bonded to each other to form a ring together with the sulfur atom to which they are bonded. 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 include a phenylene group and a naphthylene group. R II2 and R II3 Examples of the hydrocarbon group represented by include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these. R II4 Examples of the halogen atom represented by 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 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 Examples of the divalent linking group represented by A A II1 include, for example, a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O-, -S-, or -CO-. Specifically, examples are the same as those of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X III3 Examples of the structural unit containing the cation in formula (II-1-1) include the structural unit represented below and a structural unit in which a group corresponding to the methyl group of R

[0230] is replaced by a hydrogen atom, a fluorine atom, a trifluoromethyl group, etc. II4 TIFF0007704551000149.tif84130

[0231] A - Examples of the organic anion represented by A include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, carboxylic acid anions, and the like. A - As the organic anion represented by A, a sulfonate anion is preferable, and as the sulfonate anion, it is more preferable that it is an anion contained in the salt represented by the aforementioned formula (B1).

[0232] A - Examples of the sulfonylimide anion represented by A include the following. TIFF0007704551000150.tif36135

[0233] Examples of the sulfonylmethide anion include the following. TIFF0007704551000151.tif29123

[0234] Examples of the carboxylic acid anion include the following. TIFF0007704551000152.tif42154

[0235] Examples of the structural unit represented by the formula (II-1-1) include structural units represented by the following. TIFF0007704551000153.tif90154 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% with respect to all the structural units of the resin (A).

[0236] The resin (A) may have a structural unit other than the above-described structural unit, and examples of such a structural unit include structural units well-known in the art.

[0237] Resin (A) is preferably a resin composed of structural unit (a1) and structural unit (s). Structural unit (a1) is preferably at least one selected from the group consisting of structural unit (a1-0), structural unit (a1-1), and structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group), more preferably at least two, and still more preferably structural unit (a1-1) and / or structural unit (a1-2). Structural unit (s) is preferably at least one selected from the group consisting of structural unit (a2) and structural unit (a3). Structural unit (a2) is preferably a structural unit represented by formula (a2-A) or a structural unit represented by formula (a2-1). Structural unit (a3) is preferably at least one selected from the group consisting of a structural unit represented by formula (a3-1), a structural unit represented by formula (a3-2), and a structural unit represented by formula (a3-4).

[0238] Each structural unit constituting 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 a monomer that leads to these structural units. The content of each structural unit of resin (A) can be adjusted by the amount of the monomer used in the polymerization. The weight average molecular weight of resin (A) is preferably 2,000 or more (more preferably 2,500 or more, still more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or less, still more preferably 15,000 or less). In this specification, the weight average molecular weight is a value determined under the conditions described in the examples by gel permeation chromatography.

[0239] <Resin other than resin (A)> The resist composition of the present invention may use a resin other than resin (A) in combination. Examples of the resin other than resin (A) include resins containing structural unit (a4) or structural unit (a5) (hereinafter sometimes referred to as resin (X)). Among them, a resin containing structural unit (a4) is preferred as resin (X). In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 45 mol% or more based on the total of all the structural units of the resin (X). Examples of the structural unit that the resin (X) may further have include the structural unit (a2), the structural unit (a3), and the structural unit derived from other known monomers. Among them, the resin (X) is preferably a resin composed of only the structural unit (a4) and / or the structural unit (a5), and more preferably a resin composed of only the structural unit (a4). Each structural unit constituting the resin (X) may be used alone or in combination of two or more, and can be produced by a known polymerization method (for example, radical polymerization method) using the monomers that induce these structural units. The content of each structural unit of the resin (X) can be adjusted by the amount of the monomers used in the polymerization. The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The measuring means for the weight average molecular weight of the resin (X) is the same as that of the resin (A). When the resist composition contains the resin (X), its content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, even more preferably 1 to 40 parts by mass, still more preferably 1 to 30 parts by mass, and particularly preferably 1 to 8 parts by mass with respect to 100 parts by mass of the resin (A).

[0240] The content 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 the resist composition contains a resin other than the resin (A), the total content 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. The solid content of the resist composition and the content of the resin with respect thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0241] <Solvent (E)> The content of the solvent (E) 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 in the resist composition. 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; etc. One kind of the solvent (E) may be used alone, or two or more kinds may be used.

[0242] <Quencher (C)> The quencher (C) includes basic nitrogen-containing organic compounds or salts that generate an acid with a lower acidity than the acid generated from the acid generator (B) (however, carboxylic acid salts represented by formula (I) are excluded). 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, further 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.

[0243] 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). TIFF0007704551000154.tif89165

[0244] Examples of the weak acid inner salt (D) include the following salts. TIFF0007704551000155.tif72165

[0245] 〈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 is no particular limitation on the other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc. can be used.

[0246] 〈Preparation of Resist Composition〉 The resist composition of the present invention can be prepared by mixing a carboxylate (I), a resin (A), an acid generator (B), and, if necessary, a resin other than the resin (A), a solvent (E), a quencher (C), and other components (F). The mixing order is arbitrary and is not particularly limited. The temperature during mixing can be appropriately selected from 10 to 40°C according to the type of resin, etc. and the solubility of the resin, etc. in the solvent (E). The mixing time can be appropriately selected from 0.5 to 24 hours according to the mixing temperature. Note that the mixing means is also not particularly limited, and stirring and mixing, etc. can be used. After mixing the respective components, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

[0247] 〈Method for Manufacturing Resist Pattern〉 The method for manufacturing a resist pattern of the present invention (1) A step of applying the resist composition of the present invention onto a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the exposed composition layer, and (5) A step of developing the heated composition layer. To apply the resist composition onto a substrate, it can be performed by a commonly used apparatus such as a spin coater. Examples of the substrate include inorganic substrates such as silicon wafers. Before applying the resist composition, the substrate may be washed, or an antireflection film, etc. may be formed on the substrate. By drying the applied composition, the solvent is removed to form a composition layer. The drying is carried out, 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 F2 excimer laser (wavelength 157 nm), those that convert the 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., various ones can be used. In this specification, irradiating these radiations may be collectively referred to as "exposure". During exposure, usually, exposure is carried out through a mask corresponding to the required pattern. When the exposure light source is an electron beam, exposure may be carried out by direct drawing without using a mask. The exposed composition layer is heat-treated (so-called post-exposure bake) to promote the deprotection reaction in the acid-labile group. The heating temperature is usually about 50 to 200 °C, preferably about 70 to 150 °C. The heated composition layer is usually developed using a developing solution with a developing device. Examples of the developing method include the dip method, the paddle method, the spray method, the 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 small amount of water. During development, the 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.

[0248] <Usage> The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or a resist composition for EUV exposure, particularly as a resist composition for electron beam (EB) exposure or a resist composition for EUV exposure, and is useful for semiconductor microfabrication.

Examples

[0249] The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or the amount used are based on mass unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography. The analysis conditions for gel permeation chromatography are as follows. Column: TSKgel Multipore HXL-M x 3 + guard column (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI detector Column temperature: 40 °C Injection volume: 100 μl Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation) The structure of the compound was confirmed by measuring the molecular ion peak using mass spectrometry (LC is Agilent model 1100, MASS is Agilent LC / MSD model). In the following examples, the value of this molecular ion peak is indicated by “MASS”.

[0250] 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 obtain 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 obtain 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, 1.82 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 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, stirred at 23 °C for 30 minutes, then the supernatant was removed and concentrated to obtain 1.66 parts of the salt represented by formula (I-2-f). 0.95 part of the salt represented by TIFF0007704551000158.tif31150 (I-2-f) and 30 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. Then, 0.16 part of potassium carbonate and 0.05 part of potassium iodide were added, and the temperature was raised to 75°C. To the resulting mixture, 1.14 parts of the compound represented by the formula (I-2-g) were added, and the mixture was stirred at 75°C for 5 hours and then cooled to 23°C. To the resulting mixture, 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added and stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.19 parts of the compound represented by the formula (I-2-h) were obtained. 0.98 part of the salt represented by TIFF0007704551000159.tif59140 (I-2-h), 0.47 part of the salt represented by the formula (I-2-g), 30 parts of chloroform and 15 parts of ethyl acetate were mixed and stirred at 23°C for 2 hours. To the resulting mixture, 20 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.09 parts of the salt represented by the formula (I-2) were obtained. MASS(ESI(+)Spectrum):M + 579.2 MASS(ESI(-)Spectrum):M - 193.1

[0251] Example 2: Synthesis of the salt represented by the formula (I-4) 0.98 part of the salt represented by TIFF0007704551000160.tif61143 (I-2-h), 0.70 part of the salt represented by the formula (I-4-g), 30 parts of chloroform and 15 parts of ethyl acetate were mixed and stirred at 23°C for 2 hours. To the resulting mixture, 20 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.31 parts of the salt represented by the formula (I-4) were obtained. MASS(ESI(+)Spectrum):M+ 579.2 MASS(ESI(-)Spectrum):M - 337.1

[0252] Example 3: Synthesis of the salt represented by formula (I-542) 0.95 part of the salt represented by formula (I-2-f) and 30 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. Then, 0.16 part of potassium carbonate and 0.05 part of potassium iodide were added, and the temperature was raised to 75°C. To the resulting mixture, 1.61 parts of the compound represented by formula (I-542-g) were added, and the mixture was stirred at 75°C for 5 hours and then cooled to 23°C. To the resulting mixture, 50 parts of chloroform and 20 parts of 5% aqueous oxalic acid solution were added and stirred at 23°C for 30 minutes, and then the layers were separated to take out the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes, and then the layers were separated to take out the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.44 parts of the compound represented by formula (I-542-h) were obtained. 1.14 parts of the salt represented by formula (I-542-h), 0.47 part of the salt represented by formula (I-2-g), 30 parts of chloroform and 15 parts of ethyl acetate were mixed and stirred at 23°C for 2 hours. To the resulting mixture, 20 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes, and then the layers were separated to take out the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.22 parts of the salt represented by formula (I-542) were obtained. MASS(ESI(+)Spectrum):M + 679.3 MASS(ESI(-)Spectrum):M - 193.1

[0253] Example 4: Synthesis of the salt represented by formula (I-2474) 1.90 parts of the compound represented by formula (I-2-d) and 20 parts of tetrahydrofuran were mixed and stirred at 23 °C for 30 minutes, then cooled to 5 °C, and 0.28 part of sodium hydride was added. To the resulting mixture, 1.92 parts of the salt represented by formula (I-2474-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 2.26 parts of the salt represented by formula (I-2474-f). 1.24 parts of the salt represented by formula (I-2474-f) and 50 parts of dimethylformamide were mixed and stirred at 23 °C for 30 minutes, then 0.32 part of potassium carbonate and 0.10 part of potassium iodide were added, and the temperature was raised to 75 °C. To the resulting mixture, 1.14 parts of the compound represented by formula (I-2-g) was added, and the mixture was stirred at 75 °C for 5 hours, then cooled to 23 °C. To the resulting mixture, 50 parts of chloroform and 20 parts of 5% aqueous oxalic acid solution were added and 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, 1.78 parts of the compound represented by formula (I-2474-b) was obtained. 1.48 parts of the salt represented by formula (I-2474-b), 0.70 part of the salt represented by formula (I-4-g), 30 parts of chloroform and 15 parts of ethyl acetate were mixed and stirred at 23 °C for 2 hours. To the resulting mixture, 20 parts of ion-exchanged water was added and stirred at 23 °C for 30 minutes, then separated to obtain the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.79 parts of the salt represented by formula (I-2474) was obtained. MASS(ESI(+)Spectrum):M + 895.4 MASS(ESI(-)Spectrum):M - 337.1

[0254] Example 5: Synthesis of the salt represented by formula (I-479) 0.95 part of the compound represented by formula (I-2-d) and 20 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, 2.60 parts of the salt represented by formula (I-479-e) were added, and the mixture was stirred at 5°C for 3 hours. To the resulting mixture, 6.30 parts of 1N hydrochloric acid were 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 after stirring at 23°C for 30 minutes, the layers were separated and the organic layer was taken out. 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 after stirring at 23°C for 30 minutes, the supernatant was removed and concentrated to obtain 2.11 parts of the salt represented by formula (I-479-f). 1.27 parts of the salt represented by formula (I-479-f) and 30 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes, then 0.16 part of potassium carbonate and 0.05 part of potassium iodide were added, and the temperature was raised to 75°C. To the resulting mixture, 0.57 part of the compound represented by formula (I-2-g) was added, and the mixture was stirred at 75°C for 5 hours, then cooled to 23°C. To the resulting mixture, 50 parts of chloroform and 20 parts of 5% aqueous oxalic acid solution were added and stirred at 23°C for 30 minutes, then the layers were separated and the organic layer was taken out. To the obtained organic layer, 20 parts of ion-exchanged water were added, and after stirring at 23°C for 30 minutes, the layers were separated and the organic layer was taken out. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.56 parts of the compound represented by formula (I-479-g) were obtained. 1.20 parts of the salt represented by TIFF0007704551000168.tif82145 formula (I-479-g), 0.70 parts of the salt represented by formula (I-4-g), 30 parts of chloroform and 15 parts of ethyl acetate were mixed and stirred at 23 °C for 2 hours. To the resulting mixture, 20 parts of ion-exchanged water was added and stirred at 23 °C for 30 minutes, then liquid separation was carried out to take out the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.48 parts of the salt represented by formula (I-479) was obtained. MASS(ESI(+)Spectrum):M + 715.2 MASS(ESI(-)Spectrum):M - 337.1

[0255] Example 6: Synthesis of the salt represented by formula (I-2949) 1.90 parts of the compound represented by TIFF0007704551000169.tif117150 formula (I-2-d) and 20 parts of tetrahydrofuran were mixed and stirred at 23 °C for 30 minutes, then cooled to 5 °C, and 0.28 parts of sodium hydride was added. To the resulting mixture, 2.64 parts of the salt represented by formula (I-2949-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, then liquid separation was carried out 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 2.48 parts of the salt represented by formula (I-2949-f). 1.53 parts of the salt represented by TIFF0007704551000170.tif49153 (I-2949-f) and 50 parts of dimethylformamide were mixed and stirred at 23 °C for 30 minutes. Then, 0.32 part of potassium carbonate and 0.10 part of potassium iodide were added, and the temperature was raised to 75 °C. To the resulting mixture, 1.14 parts of the compound represented by formula (I-2-g) were added, and the mixture was stirred at 75 °C for 5 hours and then cooled to 23 °C. To the resulting mixture, 50 parts of chloroform and 20 parts of 5% aqueous oxalic acid solution were added and stirred at 23 °C for 30 minutes, and then the layers were separated to obtain the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water were added and stirred at 23 °C for 30 minutes, and then the layers were separated to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated to obtain 1.89 parts of the compound represented by formula (I-2949-b). 1.68 parts of the salt represented by TIFF0007704551000171.tif115150 (I-2949-b), 0.70 part of the salt represented by formula (I-4-g), 30 parts of chloroform and 15 parts of ethyl acetate were mixed and stirred at 23 °C for 2 hours. To the resulting mixture, 20 parts of ion-exchanged water were added and stirred at 23 °C for 30 minutes, and then the layers were separated to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated to obtain 1.77 parts of the salt represented by formula (I-2949). MASS(ESI(+)Spectrum):M + 1021.3 MASS(ESI(-)Spectrum):M - 337.1

[0256] Synthesis of Resin The compounds (monomers) used in 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. TIFF0007704551000172.tif44142

[0257] Synthesis Example 1: Synthesis of Resin A1 As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-1) and monomer (a3-4-2) were used, and they were mixed so that the molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-1): monomer (a3-4-2)] was 45:14:2.5:38.5. Propylene glycol monomethyl ether acetate 1.5 times the mass of the total monomer amount was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added at 1 mol% and 3 mol%, respectively, based on the total monomer amount, and these were heated at 73 °C for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The reprecipitation operation was performed twice, and resin A1 with a weight average molecular weight of 7.8×10 3 was obtained in a yield of 69%. This resin A1 has the following structural units. TIFF0007704551000173.tif36125

[0258] Synthesis Example 2: Synthesis of Resin X1 As monomers, monomer (a5-1-1) and monomer (a4-0-12) were used, and they were mixed so that the molar ratio [monomer (a5-1-1): monomer (a4-0-12)] was 50:50. Methyl isobutyl ketone 1.2 times the mass of the total monomer amount was added to form a solution. To this solution, azobis(2,4-dimethylvaleronitrile) was added at 3 mol% based on the total monomer amount, and it was heated at 70 °C for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered, and resin X with a weight average molecular weight of 1.0×10 4 was obtained in a yield of 91%. This resin X1 has the following structural units. TIFF0007704551000174.tif3182

[0259] <Preparation of Resist Composition> As shown in Table 2, the following components were mixed, and the resulting mixture was filtered through a fluororesin filter with a pore size of 0.2 μm to prepare a resist composition.

[0260]

Table 2

[0261] <Resin> A1, X1: Resin A1, Resin X1 <Acid generator (B)> B1-21: Salt represented by formula (B1-21) B1-22: Salt represented by formula (B1-22) TIFF0007704551000176.tif2897<Carboxylate (I)> I-2: Salt represented by formula (I-2) I-4: Salt represented by formula (I-4) I-479: Salt represented by formula (I-479) I-542: Salt represented by formula (I-542) I-2474: Salt represented by formula (I-2474) I-2949: Salt represented by formula (I-2949) <Quencher (C)> IX-1 IX-2 IX-3 TIFF0007704551000177.tif69135<Solvent> Propylene glycol monomethyl ether acetate 265 parts Propylene glycol monomethyl ether 20 parts 2-Heptanone 20 parts γ-Butyrolactone 3.5 parts

[0262] <Manufacture and evaluation of resist pattern> An organic antireflection film composition (ARC-29; manufactured by Nissan Chemical Industries, Ltd.) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an organic antireflection film with a thickness of 78 nm on the wafer. Next, the above resist composition was applied (spin-coated) onto this organic antireflection film so that the film thickness after drying would be 85 nm. After application, the silicon wafer was prebaked on a direct hot plate at the temperature described in the "PB" column of Table 2 for 60 seconds to form a composition layer. The silicon wafer on which the composition layer was formed was exposed using an ArF excimer stepper for immersion lithography (XT: 1900Gi; manufactured by ASML, NA = 1.35, 3 / 4 Annular X-Y polarization) with a mask for forming a contact hole pattern (hole pitch 90 nm / hole diameter 55 nm), and the exposure dose was changed stepwise for exposure. Note that ultrapure water was used as the immersion medium. After exposure, post-exposure baking was performed on a hot plate at the temperature described in the "PEB" column of Table 2 for 60 seconds. Next, the composition layer on this silicon wafer was developed using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as the developer at 23°C for 20 seconds by the dynamic dispense method to produce a negative resist pattern.

[0263] In the resist pattern obtained after development, the exposure dose at which the hole diameter formed using the mask was 45 nm was defined as the effective sensitivity.

[0264] <Mask Error Factor (MEF) Evaluation> At the effective sensitivity, resist patterns were formed using masks with mask hole diameters (hole diameters of the light-transmitting portions of the mask) of 57 nm, 56 nm, 55 nm, 54 nm, and 53 nm (hole pitch was 90 nm in all cases). The slope of the regression line when plotting the mask hole diameter on the horizontal axis and the hole diameter of the resist pattern formed (transferred) on the substrate by exposure on the vertical axis was calculated as the MEF value. The results are shown in Table 3. The numerical values in the table indicate the MEF values.

[0265]

Table 3

Industrial Applicability

[0266] The carboxylate salt of the present invention and the resist composition containing the carboxylate salt are suitable for fine processing of semiconductors because a resist pattern having a good mask error factor (MEF) can be obtained, and are extremely useful industrially.

Claims

1. A carboxylate represented by formula (I). [In formula (I), R １ 、 R ２ and R ３ each independently represents -O-R １０ 、 -O-CO-R １０ 、 -O-CO-O-R １０ 、 -O-L １ -CO-O-R １０ respectively. L １ represents an alkanediyl group having 1 to 6 carbon atoms. R ４ 、 R ５ 、 R ６ 、 R ７ 、 R ８ and R ９ each independently represents a halogen atom, an alkyl fluoride group having 1 to 6 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-, -CO-, -S- or -SO ２ -. R １０ represents an alicyclic hydrocarbon group having one or more -OR １１ groups. When there are a plurality of R １１ 's, they may be the same as or different from each other. R １１ represents a hydrogen atom, a group represented by the formula (1a), or an acid-labile group represented by the formula (2a). 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. When m1 is 2 or more, the groups within multiple parentheses may be the same as or different from each other. m2 represents any integer from 0 to 5. When m2 is 2 or more, the groups within multiple parentheses may be the same as or different from each other. m3 represents any integer from 0 to 5. When m3 is 2 or more, the groups within the plurality of parentheses may be the same as or different from each other. When m2 or m3 is 1 or more and there are a plurality of Rs １０ they may be the same as or different from each other. m4 represents any integer from 0 to 4, and when m4 is 2 or more, the plurality of Rs ４ may be the same as or different from each other. m5 represents any integer from 0 to 4, 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 4, and when m7 is 2 or more, the plurality of Rs ７ may be the same as or different from each other. m8 represents any integer from 0 to 5, and when m8 is 2 or more, a plurality of Rs ８ may be the same as or different from each other. m9 represents any integer from 0 to 5, 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 ≤ 5, and 0 ≤ m3 + m9 ≤ 5. X ０ represents a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, and -CH 2 - in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO ２ -. (In formula (1a), Raa1, Raa2, and Raa3 each independently represent an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 2 to 8 carbon atoms, an optionally substituted alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or Raa1 and Raa2 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. naa represents 0 or 1. * represents a bond.) (In formula (2a), Raa1’ and Raa2’ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, Raa3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or Raa2’ and Raa3’ are bonded to each other to form a heterocyclic group having 3 to 20 carbon atoms together with the -C-Xa- to which they are bonded, and the -CH2- contained in the hydrocarbon group and the heterocyclic group may be replaced by -O- or -S-. Xa represents an oxygen atom or a sulfur atom. * represents a bond.)]

2. X １ , X ２ and X ３ The carboxylate according to claim 1, wherein X ３ is an oxygen atom.

3. R １０ is -OR １１ group-containing adamantyl group (R １１ represents a hydrogen atom or an acid-labile group). The carboxylate according to claim 1 or 2.

4. X ０ is an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (provided that -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, which is the carboxylate according to any one of claims 1 to 3.

5. X ０ is an alicyclic hydrocarbon group having 3 to 36 carbon atoms which may have a fluorine atom or a hydroxy group (wherein -CH 2 - included in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO ２ -).) or an aromatic hydrocarbon group having 6 carbon atoms which may have a halogen atom, a hydroxy group or a perfluoroalkyl group having 1 to 4 carbon atoms, the carboxylate according to any one of claims 1 to 4.

6. X ０ The carboxylate according to claim 4, wherein X is a group represented by formula (aa). [In formula (aa), X a and X b each independently represents -O- or -S-. X １ａ represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -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 － .

7. X ０ The carboxylate according to claim 4, wherein X is an aromatic hydrocarbon group having 6 to 36 carbon atoms and having a halogen atom, a hydroxy group or a perfluoroalkyl group having 1 to 4 carbon atoms.

8. X ０ The carboxylate according to claim 4, wherein X is a group represented by formula (bb). [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 2 - in the alkanediyl group 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 the -CH 2 - in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO ２ -. * represents the bonding position with the carbon atom of -COO － .

9. A carboxylic acid generator containing the carboxylate according to any one of Claims 1 to 8.

10. A resist composition containing the carboxylic acid generator according to Claim 9, an acid generator other than the carboxylic acid generator, and a resin having an acid-labile group.

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

12. Furthermore, the resist composition according to claim 10 or 11, which contains a resin including a structural unit having a fluorine atom.

13. (1) A step of applying the resist composition according to any one of claims 10 to 12 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 composition layer after exposure; and (5) A step of developing the composition layer after heating, A method for manufacturing a resist pattern including these steps.

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